Speeding Up Sigmatropic Shifts-To Halve or to Hold.

PubMed

Tantillo, Dean J

2016-04-19

Catalysis is common. Rational catalyst design, however, is at the frontier of chemical science. Although the histories of physical organic and synthetic organic chemistry boast key chapters involving [3s,3s] sigmatropic shifts, catalysis of these reactions is much less common than catalysis of ostensibly more complex processes. The comparative dearth of catalysts for sigmatropic shifts is perhaps a result of the perception that transition state structures for these reactions, like their reactants, are nonpolar and therefore not amenable to selective stabilization and its associated barrier lowering. However, as demonstrated in this Account, transition state structures for [3s,3s] sigmatropic shifts can in fact have charge distributions that differ significantly from those of reactants, even for hydrocarbon substrates, allowing for barriers to be decreased and rates increased. In some cases, differences in charge distribution result from the inclusion of heteroatoms at specific positions in reactants, but in other cases differences are actually induced by catalysts. Perhaps surprisingly, strategies for complexation of transition state structures that remain nonpolar are also possible. In general, the strategies for catalysis employed can be characterized as involving either mechanistic intervention, where a catalyst induces a change from the concerted mechanism expected for a [3s,3s] sigmatropic shift to a multistep process (cutting the transformation into halves or smaller pieces) whose overall barrier is decreased relative to the concerted process, or transition state complexation, where a catalyst simply binds (holds) more tightly to the transition state structure for a [3s,3s] sigmatropic shift than to the reactant, leading to a lower barrier in the presence of the catalyst. Both of these strategies can be considered to be biomimetic in that enzymes frequently induce multistep processes and utilize selective transition state stabilization for the steps involved. In addition, transition state complexation was the principle around which catalytic antibodies were originally designed. The field of catalysis of sigmatropic shifts is now ready for rational design. The studies described here all provide evidence for the origins of rate acceleration, derived in large part from the results of quantum chemical calculations, that can now be applied to the design of new catalysts for [3s,3s] and other sigmatropic shifts.

Integrated reformer and shift reactor

DOEpatents

Bentley, Jeffrey M.; Clawson, Lawrence G.; Mitchell, William L.; Dorson, Matthew H.

2006-06-27

A hydrocarbon fuel reformer for producing diatomic hydrogen gas is disclosed. The reformer includes a first reaction vessel, a shift reactor vessel annularly disposed about the first reaction vessel, including a first shift reactor zone, and a first helical tube disposed within the first shift reactor zone having an inlet end communicating with a water supply source. The water supply source is preferably adapted to supply liquid-phase water to the first helical tube at flow conditions sufficient to ensure discharge of liquid-phase and steam-phase water from an outlet end of the first helical tube. The reformer may further include a first catalyst bed disposed in the first shift reactor zone, having a low-temperature shift catalyst in contact with the first helical tube. The catalyst bed includes a plurality of coil sections disposed in coaxial relation to other coil sections and to the central longitudinal axis of the reformer, each coil section extending between the first and second ends, and each coil section being in direct fluid communication with at least one other coil section.

Catalysts and process developments for two-stage liquefaction. Third quarterly technical progress report No. 44, April 1, 1991--June 30, 1991

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

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

Research under way in this project centers upon developing and evaluating catalysts and process improvements for coal liquefaction in the two-stage close-coupled catalytic process. As documented in the previous quarterly report (Task 3.1), there was little advantage for presoaking Black Thunder coal or Martin Lake lignite in a hydrogen-donor solvent, such as tetralin, at temperatures up to 600{degrees}F prior to liquefaction at higher temperatures. The amount of decarboxylation that occurred during the presoaking of Black Thunder coal or Martin Lake lignite in tetralin in the temperature range of 400 to 600{degrees}F was also relatively small. Further experimentation was undertaken inmore » a continuous flow unit with Black Thunder coal, where the primary goal was to determine the extent of decarboxylation and changes in the structure of the unconverted coal samples. The preliminary results indicated little conversion of the feed coal to THF solubles at 600{degrees}F, although the conversion did increase with increasing temperature up to 24% at 700{degrees}F. The level of decarboxylation was also low at the above reaction temperatures. Thus, presoaking in a coal-derived solvent or even tetralin does not seem to be an effective means to achieve decarboxylation. A suitable sample of Illinois No. 6 coal was received and tested for liquefaction. The batch liquefaction showed that this sample had good reactivity. The continuous liquefaction test was done in a two-stage unit with AMOCAT{trademark}-1C catalyst in both reactors. A significant amount of resid was produced throughout this three-week run. As the catalyst aged, the distillate production decreased and its product quality got worse. The feedstock liquefaction studies for the three feedstocks (Black Thunder subbituminous coal, Martin Lake lignite, and Illinois No. 6 coal) have been completed, and their results will be compared in a subsequent quarterly report.« less

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

Undergraduate research studies program at participating institutions of the HBCU Fossil Energy Consortium

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

Bhatia, S.C.; Cardelino, B.H.; Hall, J.H. Jr.

1990-01-31

This report consists of five quarterly progress reports from four participating universities. The titles of the projects are: Competition of NO and SO{sub 2} for OH generated within electrical aerosol analyzers; Dispersed iron catalysts for coal gasification; Catalytic gasification of coal chars by potassium sulfate and ferrous sulfate mixtures; Removal of certain toxic heavy metal ions in coal conversion process wastewaters; and Study of coal liquefaction catalysts. All reports have been indexed separately for inclusion on the data base. (CK)

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

Rabo, J.A.

Eight catalysts were tested from November, 1983 through January, 1984. One catalyst had only water gas shift activity. The other seven catalysts had Fischer-Tropsch synthesis activity from cobalt/thorium intimately mixed with either UCC-101 or UCC-103. This intimate mixture, either alone or promoted with X/sub 4/ or X/sub 6/, was then used by itself or used with other physically added shape selective and water gas shift components. The over-riding feature of these catalysts was the high degree of stability achieved from the intimate mixing of the metal component with UCC-103. The intimate mixing of the Co/Th with the UCC-101 or UCC-103more » gave other characteristics to these catalysts that were not seen in their physically mixed versions. On the positive side, these intimately mixed catalysts produced liquid hydrocarbons that contained less suspended wax and had a lower olefin content. On the negative side, these intimately mixed catalysts had significantly lower water gas shift activities. The incorporation of a second shape selective component or of other ingredients to the intimately mixed Co/Th+UCC-103 constituent was even less satisfactory. It should be understood that these initial drawbacks for the intimately mixed catalysts are far less important than their achievement of obtaining good stability. Such stability was one of the major goals of this contract. Such stability was one of the major goals of this contract. Its accomplishment is a major milestone towards the development of an improved Fischer-Tropsch catalyst. Appendix B has been entered individually into EDB and ERA.« less

Catalysts and process developments for two-stage liquefaction. Fourth quarterly technical progress report, July 1, 1991--September 30, 1991

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

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

Research under way in this project centers upon developing and evaluating catalysts and process improvements for coal liquefaction in the two-stage close-coupled catalytic process. As documented in the previous quarterly report there was little advantage for presoaking Black Thunder coal or Martin Lake lignite in a hydrogen-donor solvent, such as tetralin, at temperatures up to 600{degrees}F prior to liquefaction at higher temperatures. The amount of decarboxylation that occurred during the presoaking of Black Thunder coal or Martin Lake lignite in tetralin in the temperature range of 400 to 600{degrees}F was also relatively small. As indicated by both CO{sub 2} releasemore » and the change in oxygen-containing coal functionality, the level of decarboxylation in coal-derived solvent seems to correlate with the depth of coal dissolution. The feedstock liquefaction studies for the three feedstocks (Black Thunder subbituminous coal, Martin Lake lignite, and Illinois No. 6 coal) have been completed, and their results were compared in this report. Both Black Thunder coal and Martin Lake lignite gave lighter products than Illinois No. 6 coal at similar process conditions. Severe catalyst deactivation in the first stage was also observed with the Martin Lake lignite run. The first stage catalyst testing program was started. After a successful reference run with Illinois No. 6 coal, a high temperature run with AMOCAT{trademark} 1C was completed. In addition, a run was made with Illinois No. 6 coal using an oil-soluble catalyst, Molyvan L, in the first stage and AMOCAT{trademark} 1C in the second stage, where preliminary run results look promising.« less

Computational Modeling and Experimental Studies on NO(x) Reduction Under Pulveerized Coal Combustion Conditions. Quarterly technical progress report, July 1 - September 30, 1997

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

Kumpaty, S.K.; Subramanian, K.; Darboe, A.

1997-12-31

Several experiments were conducted during this quarter to study the NO{sub x} reduction effectiveness of lignite coal, activated carbon and catalytic sites such as calcium sulfide and calcium carbide. While some of the coals/chemicals could be fed easily, some needed the mixing with silica gel to result in a uniform flow through the feeder. Several trial runs were performed to ensure proper feeding of the material before conducting the actual experiment to record NO{sub x} reduction. The experimental approach has been the same as presented in the past two quarterly reports with the coal reburning experiments. Partial reduction is achievedmore » through methane addition for SR2=0.95 conditions and then coal or the catalyst is introduced to see if there is further reduction. Presented below are the results of the experiments conducted during this quarter.« less

Commercial-scale demonstration of the Liquid Phase Methanol (LPMEOH{trademark}) process. Technical progress report number 11, January 1--March 31, 1997

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

NONE

1997-06-11

During this quarter, the third draft of the Topical Report on Process Economics Studies was issued for review. A recommendation to continue with design verification testing on the coproduction of methanol and dimethyl ether (DME) was made. A liquid phase dimethyl ether (LPDME) catalyst system with reasonable long-term activity and stability is being developed, and a decision to proceed with a proof-of-concept test run at the LaPorte Alternative Fuels Development Unit (AFDU) is pending the release of a memo from Air Products on the catalyst targets and corresponding economics for a commercially successful LPDME catalyst. The off-site product-use test planmore » is to be updated in June of 1997. During this quarter, Air Products and Acurex Environmental Corporation continued developing the listing of product-use test participants who are involved in fuel cell, transportation, and stationary power plant applications. Start-up activities (Task 3.1) began during the reporting period, and coal-derived synthesis gas (syngas) was introduced to the demonstration unit. The recycle compressor was tested successfully on syngas at line pressure of 700 psig, and the reactor loop reached 220 C for carbonyl burnout. Iron carbonyl in the balanced gas feed remained below the 10 ppbv detection limit for all samples but one. Within the reactor loop, iron carbonyl levels peaked out near 200 ppbv after about 40 hours on-stream, before decreasing to between 10--20 ppbv at 160 hours on -stream. Nickel carbonyl measurements reached a peak of about 60 ppbv, and decreased at all sampling locations to below the 10 ppbv detection limit by 70 hours on-stream. Catalyst activation of the nine 2,250 lb batches required for the initial catalyst charge began and concluded. All batches met or slightly exceeded the theoretical maximum uptake of 2.82 SCF of reducing gas/lb catalyst.« less

Catalysts synthesized by selective deposition of Fe onto Pt for the water-gas shift reaction

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

Aragao, Isaias Barbosa; Ro, Insoo; Liu, Yifei

FePt bimetallic catalysts with intimate contact between the two metals were synthesized by controlled surface reactions (CSR) of (cyclohexadiene)iron tricarbonyl with hydrogen-treated supported Pt nanoparticles. Adsorption of the iron precursor on a Pt/SiO2 catalyst was studied, showing that the Fe loading could be increased by performing multiple CSR cycles, and the efficiency of this process was linked to the renewal of adsorption sites by a reducing pretreatment. The catalytic activity of these bimetallic catalysts for the water gas shift reaction was improved due to promotion by iron, likely linked to H2O activation on FeOx species at or near the Ptmore » surface, mostly in the (II) oxidation state.« less

Catalysts synthesized by selective deposition of Fe onto Pt for the water-gas shift reaction

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

Aragao, Isaias Barbosa; Ro, Insoo; Liu, Yifei

FePt bimetallic catalysts with intimate contact between the two metals were synthesized by controlled surface reactions (CSR) of (cyclohexadiene)iron tricarbonyl with hydrogen-treated supported Pt nanoparticles. Adsorption of the iron precursor on a Pt/SiO 2 catalyst was studied, showing that the Fe loading could be increased by performing multiple CSR cycles, and the efficiency of this process was linked to the renewal of adsorption sites by a reducing pretreatment. Here, the catalytic activity of these bimetallic catalysts for the water gas shift reaction was improved due to promotion by iron, likely linked to H 2O activation on FeO x species atmore » or near the Pt surface, mostly in the (II) oxidation state.« less

Catalysts synthesized by selective deposition of Fe onto Pt for the water-gas shift reaction

DOE PAGES

Aragao, Isaias Barbosa; Ro, Insoo; Liu, Yifei; ...

2017-10-04

FePt bimetallic catalysts with intimate contact between the two metals were synthesized by controlled surface reactions (CSR) of (cyclohexadiene)iron tricarbonyl with hydrogen-treated supported Pt nanoparticles. Adsorption of the iron precursor on a Pt/SiO 2 catalyst was studied, showing that the Fe loading could be increased by performing multiple CSR cycles, and the efficiency of this process was linked to the renewal of adsorption sites by a reducing pretreatment. Here, the catalytic activity of these bimetallic catalysts for the water gas shift reaction was improved due to promotion by iron, likely linked to H 2O activation on FeO x species atmore » or near the Pt surface, mostly in the (II) oxidation state.« less

Astronaut William Gregory prepares to exit his sleep quarters

NASA Technical Reports Server (NTRS)

1995-01-01

Astronaut William G. Gregory, STS-67 pilot, ejects a cassette and prepares to bail out of his sleep quarters aboard the Earth orbiting Space Shuttle Endeavour. The astronaut was about to begin a shift of support to the red team.

Investigation of syngas interaction in alcohol synthesis catalysts. Quarterly technical progress report, September 1, 1993--January 31, 1994

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

Not Available

1994-02-10

The project establishes the necessary experiment and laboratory facilities at Xavier University. This phase of the work has taken a considerable amount of time, due to the limited laboratory space and the involved administrative policies and procedures in procuring the necessary chemicals, glassware and auxiliary supplies. Though there still remain some minor problems with space, the laboratory is now equipped for preparation of catalysts. During this period, the authors focused their attention toward analyzing the magnetic nature of extensively used trimetallic catalyst system Cu-Co-Cr for the production of higher alcohols. The authors decided to investigate the effect of method ofmore » preparation and intermetallic ratio on the magnetic behavior of the system.« less

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

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

Lai, Qinghua; Skoglund, Michael D.; Zhang, Chen

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

Attrition resistant catalysts for slurry-phase Fischer-Tropsch process

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

K. Jothimurugesan

1999-11-01

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. Iron-based (Fe) catalysts are preferred catalysts for F-T because they are relatively inexpensive and possess reasonable activity for F-T synthesis (FTS). Their most advantages trait is their high water-gas shift (WGS) activity compared to their competitor, namely cobalt. This enables Fe F-T catalysts to process lowmore » H{sub 2}/CO ratio synthesis gas without an external shift reaction step. However, a serious problem with the use of Fe catalysts in a SBCR is their tendency to undergo attrition. This can cause fouling/plugging of downstream filters and equipment, make the separation of catalyst from the oil/wax product very difficult if not impossible, an d result in a steady loss of catalyst from the reactor. 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.« less

Sensitivity of Fischer-Tropsch Synthesis and Water-Gas Shift Catalysts to Poisons from High-Temperature High-Pressure Entrained-Flow (EF) Oxygen-Blown Gasifier Gasification of Coal/Biomass Mixtures

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

Burton Davis; Gary Jacobs; Wenping Ma

2011-09-30

There has been a recent shift in interest in converting not only natural gas and coal derived syngas to Fischer-Tropsch synthesis products, but also converting biomass-derived syngas, as well as syngas derived from coal and biomass mixtures. As such, conventional catalysts based on iron and cobalt may not be suitable without proper development. This is because, while ash, sulfur compounds, traces of metals, halide compounds, and nitrogen-containing chemicals will likely be lower in concentration in syngas derived from mixtures of coal and biomass (i.e., using entrained-flow oxygen-blown gasifier gasification gasification) than solely from coal, other compounds may actually be increased.more » Of particular concern are compounds containing alkali chemicals like the chlorides of sodium and potassium. In the first year, University of Kentucky Center for Applied Energy Research (UK-CAER) researchers completed a number of tasks aimed at evaluating the sensitivity of cobalt and iron-based Fischer-Tropsch synthesis (FT) catalysts and a commercial iron-chromia high temperature water-gas shift catalyst (WGS) to alkali halides. This included the preparation of large batches of 0.5%Pt-25%Co/Al{sub 2}O{sub 3} and 100Fe: 5.1Si: 3.0K: 2.0Cu (high alpha) catalysts that were split up among the four different entities participating in the overall project; the testing of the catalysts under clean FT and WGS conditions; the testing of the Fe-Cr WGS catalyst under conditions of co-feeding NaCl and KCl; and the construction and start-up of the continuously stirred tank reactors (CSTRs) for poisoning investigations. In the second and third years, researchers from the University of Kentucky Center for Applied Energy Research (UK-CAER) continued the project by evaluating the sensitivity of a commercial iron-chromia high temperature water-gas shift catalyst (WGS) to a number of different compounds, including KHCO{sub 3}, NaHCO{sub 3}, HCl, HBr, HF, H{sub 2}S, NH{sub 3}, and a combination of H{sub 2}S and NH{sub 3}. Cobalt and iron-based Fischer-Tropsch synthesis (FT) catalysts were also subjected to a number of the same compounds in order to evaluate their sensitivities at different concentration levels of added contaminant.« less

Cationic Cyclizations and Rearrangements Promoted by a Heterogeneous Gold Catalyst

PubMed Central

2015-01-01

A heterogeneous gold catalyst with remarkable activity for promoting the electrophilic reactions of aryl vinyl ketones and aryl dienyl ketones is described. The catalyst is easy to prepare, is robust, and can be recycled. Low loadings are effective for different types of cationic reactions, including Nazarov cyclizations, lactonizations, and [1,2] shifts. PMID:24432741

Sensitivity of Fischer-Tropsch Synthesis and Water-Gas Shift Catalystes to Poisons form High-Temperature High-Pressure Entrained-Flow (EF) Oxygen-Blown Gasifier Gasification of Coal/Biomass Mixtures

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

Burton Davis; Gary Jacobs; Wenping Ma

2009-09-30

There has been a recent shift in interest in converting not only natural gas and coal derived syngas to Fischer-Tropsch synthesis products, but also converting biomass-derived syngas, as well as syngas derived from coal and biomass mixtures. As such, conventional catalysts based on iron and cobalt may not be suitable without proper development. This is because, while ash, sulfur compounds, traces of metals, halide compounds, and nitrogen-containing chemicals will likely be lower in concentration in syngas derived from mixtures of coal and biomass (i.e., using entrained-flow oxygen-blown gasifier gasification gasification) than solely from coal, other compounds may actually be increased.more » Of particular concern are compounds containing alkali chemicals like the chlorides of sodium and potassium. In the first year, University of Kentucky Center for Applied Energy Research (UK-CAER) researchers completed a number of tasks aimed at evaluating the sensitivity of cobalt and iron-based Fischer-Tropsch synthesis (FT) catalysts and a commercial iron-chromia high temperature water-gas shift catalyst (WGS) to alkali halides. This included the preparation of large batches of 0.5%Pt-25%Co/Al{sub 2}O{sub 3} and 100Fe: 5.1Si: 3.0K: 2.0Cu (high alpha) catalysts that were split up among the four different entities participating in the overall project; the testing of the catalysts under clean FT and WGS conditions; the testing of the Fe-Cr WGS catalyst under conditions of co-feeding NaCl and KCl; and the construction and start-up of the continuously stirred tank reactors (CSTRs) for poisoning investigations.« less

Highly Effective Pt-Based Water-Gas Shift Catalysts by Surface Modification with Alkali Hydroxide Salts

DOE PAGES

Kusche, Matthias; Bustillo, Karen; Agel, Friederike; ...

2015-01-29

Here, we describe an economical and convenient method to improve the performance of Pt/alumina catalysts for the water–gas shift reaction through surface modification of the catalysts with alkali hydroxides according to the solid catalyst with ionic liquid layer approach. The results are in agreement with our findings reported earlier for methanol steam reforming. This report indicates that alkali doping of the catalyst plays an important role in the observed catalyst activation. In addition, the basic and hygroscopic nature of the salt coating contributes to a significant improvement in the performance of the catalyst. During the reaction, a partly liquid filmmore » of alkali hydroxide forms on the alumina surface, which increases the availability of H 2O at the catalytically active sites. Kinetic studies reveal a negligible effect of the KOH coating on the rate dependence of CO and H 2O partial pressures. In conclusion, TEM studies indicate an agglomeration of the active Pt clusters during catalyst preparation; restructuring of Pt nanoparticles occurs under reaction conditions, which leads to a highly active and stable system over 240h time on stream. Excessive pore fillings with KOH introduce a mass transfer barrier as indicated in a volcano-shaped curve of activity versus salt loading. The optimum KOH loading was found to be 7.5wt%.« less

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

Winter, Lea R.; Gomez, Elaine; Yan, Binhang

CO 2 hydrogenation over Fe-modified Ni/CeO 2 catalysts was investigated in a batch reactor using time-resolved in situ FTIR spectroscopy. Low loading of Ni/CeO 2 was associated with high selectivity to CO over CH 4, while higher Ni loading improved CO 2 hydrogenation activity with a reduced CO selectivity. X-ray absorption near-edge structure (XANES) analysis revealed Ni to be metallic for all catalysts including the CO-selective low loading 0.5% Ni catalyst, suggesting that the selectivity trend is due to structural rather than oxidation state effects. The loading amount of 1.5% Ni was selected for co-impregnation with Fe, based on themore » significant shift in product selectivity towards CH 4 for that loading amount, in order to shift the selectivity towards CO while maintaining high activity. Temperature programmed reduction (TPR) results indicated bimetallic interactions between Ni and Fe, and XANES analysis showed that about 70% of Fe in the bimetallic catalysts was oxidized. The Ni-Fe catalysts demonstrated improved selectivity towards CO without significantly compromising activity, coupling the high activity of Ni catalysts and the high CO selectivity of Fe. The general trends in Ni loading and bimetallic modification should guide efforts to develop non-precious metal catalysts for the selective production of CO by CO 2 hydrogenation.« less

Natural gas-assisted steam electrolyzer

DOEpatents

Pham, Ai-Quoc; Wallman, P. Henrik; Glass, Robert S.

2000-01-01

An efficient method of producing hydrogen by high temperature steam electrolysis that will lower the electricity consumption to an estimated 65 percent lower than has been achievable with previous steam electrolyzer systems. This is accomplished with a natural gas-assisted steam electrolyzer, which significantly reduces the electricity consumption. Since this natural gas-assisted steam electrolyzer replaces one unit of electrical energy by one unit of energy content in natural gas at one-quarter the cost, the hydrogen production cost will be significantly reduced. Also, it is possible to vary the ratio between the electricity and the natural gas supplied to the system in response to fluctuations in relative prices for these two energy sources. In one approach an appropriate catalyst on the anode side of the electrolyzer will promote the partial oxidation of natural gas to CO and hydrogen, called Syn-Gas, and the CO can also be shifted to CO.sub.2 to give additional hydrogen. In another approach the natural gas is used in the anode side of the electrolyzer to burn out the oxygen resulting from electrolysis, thus reducing or eliminating the potential difference across the electrolyzer membrane.

Size effects in electronic and catalytic properties of unsupported palladium nanoparticles in electrooxidation of formic acid.

PubMed

Zhou, Wei Ping; Lewera, Adam; Larsen, Robert; Masel, Rich I; Bagus, Paul S; Wieckowski, Andrzej

2006-07-13

We report a combined X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), and chronoamperometry (CA) study of formic acid electrooxidation on unsupported palladium nanoparticle catalysts in the particle size range from 9 to 40 nm. The CV and CA measurements show that the most active catalyst is made of the smallest (9 and 11 nm) Pd nanoparticles. Besides the high reactivity, XPS data show that such nanoparticles display the highest core-level binding energy (BE) shift and the highest valence band (VB) center downshift with respect to the Fermi level. We believe therefore that we found a correlation between formic acid oxidation current and BE and VB center shifts, which, in turn, can directly be related to the electronic structure of palladium nanoparticles of different particle sizes. Clearly, such a trend using unsupported catalysts has never been reported. According to the density functional theory of heterogeneous catalysis, and mechanistic considerations, the observed shifts are caused by a weakening of the bond strength of the COOH intermediate adsorption on the catalyst surface. This, in turn, results in the increase in the formic acid oxidation rate to CO2 (and in the associated oxidation current). Overall, our measurements demonstrate the particle size effect on the electronic properties of palladium that yields different catalytic activity in the HCOOH oxidation reaction. Our work highlights the significance of the core-level binding energy and center of the d-band shifts in electrocatalysis and underlines the value of the theory that connects the center of the d-band shifts to catalytic reactivity.

Molecular and Silica-Supported Molybdenum Alkyne Metathesis Catalysts: Influence of Electronics and Dynamics on Activity Revealed by Kinetics, Solid-State NMR, and Chemical Shift Analysis.

PubMed

Estes, Deven P; Gordon, Christopher P; Fedorov, Alexey; Liao, Wei-Chih; Ehrhorn, Henrike; Bittner, Celine; Zier, Manuel Luca; Bockfeld, Dirk; Chan, Ka Wing; Eisenstein, Odile; Raynaud, Christophe; Tamm, Matthias; Copéret, Christophe

2017-12-06

Molybdenum-based molecular alkylidyne complexes of the type [MesC≡Mo{OC(CH 3 ) 3-x (CF 3 ) x } 3 ] (MoF 0 , x = 0; MoF 3 , x = 1; MoF 6 , x = 2; MoF 9 , x = 3; Mes = 2,4,6-trimethylphenyl) and their silica-supported analogues are prepared and characterized at the molecular level, in particular by solid-state NMR, and their alkyne metathesis catalytic activity is evaluated. The 13 C NMR chemical shift of the alkylidyne carbon increases with increasing number of fluorine atoms on the alkoxide ligands for both molecular and supported catalysts but with more shielded values for the supported complexes. The activity of these catalysts increases in the order MoF 0 < MoF 3 < MoF 6 before sharply decreasing for MoF 9 , with a similar effect for the supported systems (MoF 0 ≈ MoF 9 < MoF 6 < MoF 3 ). This is consistent with the different kinetic behavior (zeroth order in alkyne for MoF 9 derivatives instead of first order for the others) and the isolation of stable metallacyclobutadiene intermediates of MoF 9 for both molecular and supported species. Detailed solid-state NMR analysis of molecular and silica-supported metal alkylidyne catalysts coupled with DFT/ZORA calculations rationalize the NMR spectroscopic signatures and discernible activity trends at the frontier orbital level: (1) increasing the number of fluorine atoms lowers the energy of the π*(M≡C) orbital, explaining the more deshielded chemical shift values; it also leads to an increased electrophilicity and higher reactivity for catalysts up to MoF 6 , prior to a sharp decrease in reactivity for MoF 9 due to the formation of stable metallacyclobutadiene intermediates; (2) the silica-supported catalysts are less active than their molecular analogues because they are less electrophilic and dynamic, as revealed by their 13 C NMR chemical shift tensors.

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

Not Available

The five iron catalysts reported were all promoted with potassium. The most promising results were obtained with the catalyst containing UCC-111 (Appendix B, Run 10225-3). In earlier studies UCC-111 alone had been found to be a poor Task 1 catalyst for oligomerizing propylene. Physically combined with potassium-promoted iron, however, it proved surprisingly effective as a syngas catalyst in Task 2. It produced straight-chain olefinic hydrocarbons, as a normal Fischer-Tropsch catalyst does, but unlike the normal Fischer-Tropsch catalyst, it may also have isomerized the carbon-carbon double bond. Transfer of the double bond from the usual Position 1, typical for Fischer-Tropsch products,more » to an interior position, should not only lower the pour point of the liquid product, but it should raise its octane number as well. Four of the six cobalt catalysts reported this quarter were promoted with either thorium or thorium and potassium. All six were synthesized by the precipitate-slurry method, with either LZ-105-6, LZ-Y-82, UCC-101 or UCC-107 as the Molecular Sieve component. The test results for most of these catalysts indicate that cobalt is more effective than iron in producing a high yield of motor fuels. This increase in motor fuel yield was due primarily to a higher yield of diesel oil, with the gasoline yield remaining approximately the same as for the iron catalysts. This increased diesel oil yield, as well as an increased methane yield, was balanced against a decreased C/sub 2/-C/sub 4/ yield. The yields of the heavy fractions for both metal catalysts remained relatively low.« less

Development of a practical photochemical energy storage system. Quarterly report. [Interconversion between norbornadiene and quadricyclene for thermochemical heat storage

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

Hautala, R.R.; Kutal, C.R.

1977-06-15

Research on polymeric organic sensitizers and polymeric inorganic sensitizers for the conversion of norbornadine to quadricyclene and catalysts for the conversion of quadricyclene to norbornadine is described. The interconversion of norbornadine and quadricyclene is studied for its possible use for thermochemical solar energy storage. (WHK)

Photogeneration of active formate decomposition catalysts to produce hydrogen from formate and water

DOEpatents

King, Jr., Allen D.; King, Robert B.; Sailers, III, Earl L.

1983-02-08

A process for producing hydrogen from formate and water by photogenerating an active formate decomposition catalyst from transition metal carbonyl precursor catalysts at relatively low temperatures and otherwise mild conditions is disclosed. Additionally, this process may be expanded to include the generation of formate from carbon monoxide and hydroxide such that the result is the water gas shift reaction.

Crew quarters for Space Station

NASA Technical Reports Server (NTRS)

Mount, F. E.

1989-01-01

The only long-term U.S. manned space mission completed has been Skylab, which has similarities as well as differences to the proposed Space Station. With the exception of Skylab missions, there has been a dearth of experience on which to base the design of the individual Space Station Freedom crew quarters. Shuttle missions commonly do not have sleep compartments, only 'sleeping arrangements'. There are provisions made for each crewmember to have a sleep restraint and a sleep liner, which are attached to a bulkhead or a locker. When the Shuttle flights began to have more than one working shift, crew quarters became necessary due to noise and other disturbances caused by crew task-related activities. Shuttle missions that have planned work shifts have incorporated sleep compartments. To assist in gaining more information and insight for the design of the crew quarters for the Space Station Freedom, a survey was given to current crewmembers with flight experience. The results from this survey were compiled and integrated with information from the literature covering space experience, privacy, and human-factors issues.

Tuning Ni-catalyzed CO 2 hydrogenation selectivity via Ni-ceria support interactions and Ni-Fe bimetallic formation

DOE PAGES

Winter, Lea R.; Gomez, Elaine; Yan, Binhang; ...

2017-10-16

CO 2 hydrogenation over Fe-modified Ni/CeO 2 catalysts was investigated in a batch reactor using time-resolved in situ FTIR spectroscopy. Low loading of Ni/CeO 2 was associated with high selectivity to CO over CH 4, while higher Ni loading improved CO 2 hydrogenation activity with a reduced CO selectivity. X-ray absorption near-edge structure (XANES) analysis revealed Ni to be metallic for all catalysts including the CO-selective low loading 0.5% Ni catalyst, suggesting that the selectivity trend is due to structural rather than oxidation state effects. The loading amount of 1.5% Ni was selected for co-impregnation with Fe, based on themore » significant shift in product selectivity towards CH 4 for that loading amount, in order to shift the selectivity towards CO while maintaining high activity. Temperature programmed reduction (TPR) results indicated bimetallic interactions between Ni and Fe, and XANES analysis showed that about 70% of Fe in the bimetallic catalysts was oxidized. The Ni-Fe catalysts demonstrated improved selectivity towards CO without significantly compromising activity, coupling the high activity of Ni catalysts and the high CO selectivity of Fe. The general trends in Ni loading and bimetallic modification should guide efforts to develop non-precious metal catalysts for the selective production of CO by CO 2 hydrogenation.« less

Shifting Paradigms in Music Education Research (1953-1978): A Theoretical and Quantitative Reassessment

ERIC Educational Resources Information Center

Jorgensen, Estelle R.; Ward-Steinman, Patrice Madura

2015-01-01

The purpose of this study was to examine evidence of a hypothesized shift in the operative research paradigms in music education during the first quarter century of the publication of the "Journal of Research in Music Education," during the period 1953 to 1978. This shift was from humanities-oriented historical and philosophical studies…

Exploring the activity of a novel Au/TiC(001) model catalyst towards CO and CO 2 hydrogenation

DOE PAGES

Asara, Gian Giacomo; Ricart, Josep M.; Rodriguez, Jose A.; ...

2015-02-02

Small metallic nanoparticles supported on transition metal carbides exhibit an unexpected high activity towards a series of chemical reactions. In particular, the Au/TiC system has proven to be an excellent catalyst for SO 2 decomposition, thiophene hydrodesulfurization, O 2 and H 2 dissociation and the water gas shift reaction. Recent studies have shown that Au/TiC is a very good catalyst for the reverse water–gas shift (CO 2 + H 2 → CO + H 2O) and CO 2 hydrogenation to methanol. The present work further expands the range of applicability of this novel type of systems by exploring the catalyticmore » activity of Au/TiC towards the hydrogenation of CO or CO 2 with periodic density functional theory (DFT) calculations on model systems. Hydrogen dissociates easily on Au/TiC but direct hydrogenation of CO to methanol is hindered by very high activation barriers implying that, on this model catalyst, methanol production from CO 2 involves the hydrogenation of a HOCO-like intermediate. Thus, when dealing with mixtures of syngas (CO/CO 2/H 2/H 2O), CO could be transformed into CO 2 through the water gas shift reaction with subsequent hydrogenation of CO 2 to methanol.« less

Research on solvent-refined coal. Quarterly technical progress report, April 1, 1981-June 30, 1981

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

Not Available

1981-10-01

This report describes progress on the Research on Solvent Refined Coal project by The Pittsburg and Midway Coal Mining Co.'s Merriam Laboratory during the second quarter of 1981. Alexander Mine coal was evaluated as a feedstock for major liquefaction facilities and had a yield structure similar to other reactive Pittsburgh seam coals at standard SRC II conditions. Two lots of coal from the Ireland Mine (Pittsburgh seam) were found to be of nearly the same composition and produced essentially the same yields. Two experiments in which coal-derived nonvolatile organic matter was processed without fresh coal feed indicate constant rates ofmore » conversion of SRC to oil and gas. Insoluble organic matter (IOM) remained unconverted. The naphtha and middle distillate products from the deep conversion contained less sulfur but more nitrogen than those from conventional SRC II processing. Encouraging results were obtained when a very small amount of iron oxide dispersed on alumina was added to Kaiparowits coal which cannot be processed at normal SRC II conditions without added catalyst. Subbituminous coals from the McKinley and Edna Mines were processed successfully with added pyrite but would not run when the added catalyst was removed.« less

In Situ Characterization of Mesoporous Co/CeO 2 Catalysts for the High-Temperature Water-Gas Shift

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

Vovchok, Dimitriy; Guild, Curtis J.; Dissanayake, Shanka

Here, mesoporous Co/CeO 2 catalysts were found to exhibit significant activity for the high-temperature water-gas shift (WGS) reaction with cobalt loadings as low as 1 wt %. The catalysts feature a uniform dispersion of cobalt within the CeO 2 fluorite type lattice with no evidence of discrete cobalt phase segregation. In situ XANES and ambient pressure XPS experiments were used to elucidate the active state of the catalysts as partially reduced cerium oxide doped with oxidized cobalt atoms. In situ XRD and DRIFTS experiments suggest facile cerium reduction and oxygen vacancy formation, particularly with lower cobalt loadings. In situ DRIFTSmore » analysis also revealed the presence of surface carbonate and bidentate formate species under reaction conditions, which may be associated with additional mechanistic pathways for the WGS reaction. Deactivation behavior was observed with higher cobalt loadings. XANES data suggest the formation of small metallic cobalt clusters at temperatures above 400 °C may be responsible. Notably, this deactivation was not observed for the 1% cobalt loaded catalyst, which exhibited the highest activity per unit of cobalt.« less

In Situ Characterization of Mesoporous Co/CeO 2 Catalysts for the High-Temperature Water-Gas Shift

DOE PAGES

Vovchok, Dimitriy; Guild, Curtis J.; Dissanayake, Shanka; ...

2018-04-04

Here, mesoporous Co/CeO 2 catalysts were found to exhibit significant activity for the high-temperature water-gas shift (WGS) reaction with cobalt loadings as low as 1 wt %. The catalysts feature a uniform dispersion of cobalt within the CeO 2 fluorite type lattice with no evidence of discrete cobalt phase segregation. In situ XANES and ambient pressure XPS experiments were used to elucidate the active state of the catalysts as partially reduced cerium oxide doped with oxidized cobalt atoms. In situ XRD and DRIFTS experiments suggest facile cerium reduction and oxygen vacancy formation, particularly with lower cobalt loadings. In situ DRIFTSmore » analysis also revealed the presence of surface carbonate and bidentate formate species under reaction conditions, which may be associated with additional mechanistic pathways for the WGS reaction. Deactivation behavior was observed with higher cobalt loadings. XANES data suggest the formation of small metallic cobalt clusters at temperatures above 400 °C may be responsible. Notably, this deactivation was not observed for the 1% cobalt loaded catalyst, which exhibited the highest activity per unit of cobalt.« less

Characterization of MoVTeNbO x catalysts during oxidation reactions using in situ/operando techniques: A review

DOE PAGES

Lwin, Soe; Diao, Weijian; Baroi, Chinmoy; ...

2017-04-08

The domestic fossil feedstock in recent years is shifting towards light hydrocarbons due to abundance of shale gas from hydraulic fracturing. This shift induces a need for greater flexibility in both new and existing processing plants to produce consumer products (polymers, paints, lubricants, etc.) from new feedstocks. The oxidative catalytic reactions operate at milder conditions than the processing of feedstocks through steam cracking. The conversion of light feedstocks (C3 and shorter hydrocarbons) to high value chemicals through highly selective catalysts in the presence of oxygen plays a crucial role in eliminating wastes, reducing greenhouse gas emissions and lowering market prices.more » Among all catalysts for light hydrocarbon processing through oxidation reactions, bulk mixed metal oxides such as MoVTe(Sb)NbO x catalysts are the most promising due to their performance under favorable reaction conditions (temperature, pressure, etc). Here, state-of-the-art in situ/operando techniques along with transient kinetics can revolutionize the development of catalysts by providing information about the nature of active sites, intermediates and kinetics under realistic industrial conditions. Only through detailed understanding of these catalyst behaviors can new synthesis methods be developed that will improve reactivity, selectivity and lifetimes of these catalysts. In this review, dynamic changes of this mixed oxide catalyst during the reaction (such as changes in surface composition, oxidation states, acidity, etc) are discussed mainly from knowledge and insights obtained from these in situ/operando approaches. The most common oxidation reactions driven by the MoVTeNbO x catalysts and studied under operando/in situ conditions to be discussed here are: (1) oxidative dehydrogenation of light alkanes (ethane and propane), (2) propane ammoxidation to acrylonitrile and (3) selective oxidation of propane to acrylic acid.« less

Characterization of MoVTeNbO x catalysts during oxidation reactions using in situ/operando techniques: A review

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

Lwin, Soe; Diao, Weijian; Baroi, Chinmoy

The domestic fossil feedstock in recent years is shifting towards light hydrocarbons due to abundance of shale gas from hydraulic fracturing. This shift induces a need for greater flexibility in both new and existing processing plants to produce consumer products (polymers, paints, lubricants, etc.) from new feedstocks. The oxidative catalytic reactions operate at milder conditions than the processing of feedstocks through steam cracking. The conversion of light feedstocks (C3 and shorter hydrocarbons) to high value chemicals through highly selective catalysts in the presence of oxygen plays a crucial role in eliminating wastes, reducing greenhouse gas emissions and lowering market prices.more » Among all catalysts for light hydrocarbon processing through oxidation reactions, bulk mixed metal oxides such as MoVTe(Sb)NbO x catalysts are the most promising due to their performance under favorable reaction conditions (temperature, pressure, etc). Here, state-of-the-art in situ/operando techniques along with transient kinetics can revolutionize the development of catalysts by providing information about the nature of active sites, intermediates and kinetics under realistic industrial conditions. Only through detailed understanding of these catalyst behaviors can new synthesis methods be developed that will improve reactivity, selectivity and lifetimes of these catalysts. In this review, dynamic changes of this mixed oxide catalyst during the reaction (such as changes in surface composition, oxidation states, acidity, etc) are discussed mainly from knowledge and insights obtained from these in situ/operando approaches. The most common oxidation reactions driven by the MoVTeNbO x catalysts and studied under operando/in situ conditions to be discussed here are: (1) oxidative dehydrogenation of light alkanes (ethane and propane), (2) propane ammoxidation to acrylonitrile and (3) selective oxidation of propane to acrylic acid.« less

Mechanism of catalytic gasification of coal char. Quarterly technical report No. 5, October 1 to December 31, 1981

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

Wood, B. J.; Sancier, K. M.; Sheridan, D. R.

1982-02-26

The purpose of this study is to determine the mechanisms involved in the catalytic reactions of coal char and to identify the specific reaction steps and the parameters that control the catalytic process. The mode of action of the catalyst can be viewed in two ways. In one view, the catalyst participates in a reduction/oxidation cycle. The initial reaction between the carbon and the catalyst reduces the KOH to potassium accompanied by the gaseous reactant (H/sub 2/O or CO/sub 2/), producing further gaseous products (CO and H/sub 2/) and regenerating the initial state of the catalyst. In an alternative view,more » the catalyst initially forms an alkali metal addition compound with the carbon network of the char. The carbon-carbon bonds are altered by the formation of the metal-carbon linkage, possibly by electron transfer from the alkali metal atom to the carbon structure. As a result, the carbon structure is more readily attacked by the gaseous reactant (CO or H/sub 2/O) to produce the products of gasification. The following areas were investigated to provide experimental evidence for these catalytic modes of action: chemical kinetic measurements; thermodynamic measurements; free radicals in reacting carbon; electrical conductivity measurements. A detailed discussion on the catalyst-carbon interaction and on the reaction intermediate is provided.« less

When Is Russia Joining NATO Russian Security Orientation in the Twenty-first Century

DTIC Science & Technology

2010-06-01

around the world and makes its products - ranging from textual translations to multimedia productions - available to customers throughout the United...of economic, political, and social restructuring, became the unintended catalyst for dismantling what had taken nearly three-quarters of a century... dissatisfaction with Russia. The most vocal and sensitive nations are the Baltic nations. This tension will be challenging for NATO-Russia

Ceria-based model catalysts: fundamental studies on the importance of the metal–ceria interface in CO oxidation, the water–gas shift, CO 2 hydrogenation, and methane and alcohol reforming

DOE PAGES

Rodriguez, José A.; Grinter, David C.; Liu, Zongyuan; ...

2017-02-17

Model metal/ceria and ceria/metal catalysts have been shown to be excellent systems for studying fundamental phenomena linked to the operation of technical catalysts. In the last fifteen years, many combinations of well-defined systems involving different kinds of metals and ceria have been prepared and characterized using the modern techniques of surface science. So far most of the catalytic studies have been centered on a few reactions: CO oxidation, the hydrogenation of CO 2, and the production of hydrogen through the water–gas shift reaction and the reforming of methane or alcohols. By using model catalysts it is been possible to examinemore » in detail correlations between the structural, electronic and catalytic properties of ceria–metal interfaces. In situ techniques (X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, infrared spectroscopy, scanning tunneling microscopy) have been combined to study the morphological changes under reaction conditions and investigate the evolution of active phases involved in the cleavage of C–O, C–H and C–C bonds. Several studies with model ceria catalysts have shown the importance of strong metal–support interactions. Generally, a substantial body of knowledge has been acquired and concepts have been developed for a more rational approach to the design of novel technical catalysts containing ceria.« less

In-situ activation of CuO/ZnO/Al.sub.2 O.sub.3 catalysts in the liquid phase

DOEpatents

Brown, Dennis M.; Hsiung, Thomas H.; Rao, Pradip; Roberts, George W.

1989-01-01

The present invention relates to a method of activation of a CuO/ZnO/Al.sub.2 O.sub.3 catalyst slurried in a chemically inert liquid. Successful activation of the catalyst requires the use of a process in which the temperature of the system at any time is not allowed to exceed a certain critical value, which is a function of the specific hydrogen uptake of the catalyst at that same time. This process is especially critical for activating highly concentrated catalyst slurries, typically 25 to 50 wt %. Activation of slurries of CuO/ZnO/Al.sub.2 O.sub.3 catalyst is useful in carrying out the liquid phase methanol or the liquid phase shift reactions.

Highly active Pt/MoC and Pt/TiC catalysts for the low-temperature water-gas shift reaction: Effects of the carbide metal/carbon ratio on the catalyst performance

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

Rodriguez, José A.; Ramírez, Pedro J.; Gutierrez, Ramón A.

We present that Pt/MoC and Pt/TiC(001) are excellent catalysts for the low-temperature water-gas shift (WGS, CO + H 2O → H 2 + CO 2) reaction. They exhibit high-activity, stability and selectivity. The highest catalytic activities are seen for small coverages of Pt on the carbide substrates. Synergistic effects at the metal-carbide interface produce an enhancement in chemical activity with respect to pure Pt, MoC and TiC. A clear correlation is found between the ability of the Pt/MoC and Pt/TiC(001) surfaces to partially dissociate water and their catalytic activity for the WGS reaction. Finally, an overall comparison of the resultsmore » for Pt/MoC and Pt/Mo 2C(001) indicates that the metal/carbon ratio in the carbide support can have a strong influence in the stability and selectivity of WGS catalysts and is a parameter that must be taken into consideration when designing these systems.« less

Highly active Pt/MoC and Pt/TiC catalysts for the low-temperature water-gas shift reaction: Effects of the carbide metal/carbon ratio on the catalyst performance

DOE PAGES

Rodriguez, José A.; Ramírez, Pedro J.; Gutierrez, Ramón A.

2016-09-20

We present that Pt/MoC and Pt/TiC(001) are excellent catalysts for the low-temperature water-gas shift (WGS, CO + H 2O → H 2 + CO 2) reaction. They exhibit high-activity, stability and selectivity. The highest catalytic activities are seen for small coverages of Pt on the carbide substrates. Synergistic effects at the metal-carbide interface produce an enhancement in chemical activity with respect to pure Pt, MoC and TiC. A clear correlation is found between the ability of the Pt/MoC and Pt/TiC(001) surfaces to partially dissociate water and their catalytic activity for the WGS reaction. Finally, an overall comparison of the resultsmore » for Pt/MoC and Pt/Mo 2C(001) indicates that the metal/carbon ratio in the carbide support can have a strong influence in the stability and selectivity of WGS catalysts and is a parameter that must be taken into consideration when designing these systems.« less

Correlation between the Knight shift of chemisorbed CO and the Fermi level local density of states at clean platinum catalyst surfaces

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

Tong, Y.Y.; Rice, C.; Godbout, N.

1999-04-07

Due to its fundamental importance in heterogeneous catalysis, as well as in electrocatalysis, the chemisorption and reaction of CO on transition metal surfaces has been an important focus of modern surface science. Here, the NMR spectroscopy of {sup 13}CO adsorbed onto transition metal surfaces has been shown to be a very powerful probe of molecular structure and dynamics of CO itself, as well as a probe of the electronic properties of the transition metal surfaces onto which it is adsorbed. The authors have investigated the {sup 195}Pt and {sup 13}C nuclear magnetic resonance (NMR) spectroscopy of clean-surface platinum catalysts andmore » of CO chemisorbed onto Pt catalysts surfaces. They use Knight shift, relaxation, and J-coupling data to deduce information about the Fermi level local density of states (E{sub f}-LDOS) at catalyst surfaces. There is a linear correlation between the Knight shifts of chemisorbed CO and the clean surface E{sub f}-LDOS of platinum onto which the CO is bound, as determined by {sup 13}C and {sup 195}Pt NMR. The correlation amounts to {approximately} 12 ppm/Ry{sup {minus}1} {center_dot} atom{sup {minus}1}, the same as that which can be deduced for CO on palladium, as well as from the electrode potential dependence of {sup 13}C Knight shifts and infrared vibrational frequencies, {nu}{sub CO}, and the relationship between {nu}{sub CO} and the E{sub f}-LDOS at clean platinum surfaces. The ability to now directly relate meal and adsorbate electronic properties opens up new avenues for investigating metal-ligand interactions in heterogeneous catalysis and electrocatalysis.« less

Zeolite Y encapsulated with Fe-TiO2 for ultrasound-assisted degradation of amaranth dye in water.

PubMed

Alwash, Atheel Hassan; Abdullah, Ahmad Zuhairi; Ismail, Norli

2012-09-30

A new heterogeneous catalyst for sonocatalytic degradation of amaranth dye in water was synthesized by introducing titania into the pores of zeolite (NaY) through ion exchange method while Fe (III) was immobilized on the encapsulated titanium via impregnation method. XRD results could not detect any peaks for titanium oxide or Fe(2)O(3) due to its low loading. The UV-vis analysis proved a blue shift toward shorter wavelength after the loading of Ti into NaY while a red shift was detected after the loading of Fe into the encapsulated titanium. Different reaction variables such as TiO(2) content, amount of Fe, pH values, amount of hydrogen peroxide, catalyst loading and the initial dye concentration were studied to estimate their effect on the decolorization efficiency of amaranth. The maximum decolorization efficiency achieved was 97.5% at a solution pH of 2.5, catalyst dosage of 2 g/L, 20 mmol/100 mL of H(2)O(2) and initial dye concentration of 10 mg/L. The new heterogeneous catalyst Fe/Ti-NaY was a promising catalyst for this reaction and showed minimum Fe leaching at the end of the reaction. Copyright © 2012 Elsevier B.V. All rights reserved.

In situ {sup 13}C MAS NMR study of n-hexane conversion on Pt and Pd supported on basic materials. II. On the mechanism of isomerization and hydrocracking

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

Ivanova, I.I.; Seirvert, M.; Pasau-Claerbout, A.

{sup 13}C MAS NMR spectroscopy was performed in situ to investigate the mechanisms of n-hexane isomerization and hydrocracking on Pt and Pd supported on Al-stabilized magnesia (Pt/Mg(Al)O and Pd/Mg(Al)O), and Pt on KL zeolite (Pt/KL). All the catalysts had high metal dispersion, the metal particle sizes being 13, 11, and 18 {Angstrom}, respectively. n-Hexane 1-{sup 13}C was used for in situ label tracer experiments. {sup 13}C MAS NMR spectra were obtained during the time course of the reaction at 573 and 653 K. The NMR results were then quantified, and the reaction kinetics were studied. Identification of the primary andmore » secondary labeled reaction products led to the conclusion that both cyclic and bond-shift isomerization mechanisms operate on the three catalysts. In the case of Pt/Mg(Al)O, the cyclic mechanism accounts for 80% of the isomerization products. In the case of Pt/KL and Pd/Mg(Al)O, the contribution of bond-shift reactions increases due to restricted formation of the methylcyclopentane intermediate on the former and to suppressed hydrogenolysis of methylcyclopentane on the latter. A nonselective cyclic isomerization mechanism operates on magnesia catalysts, while on Pt/KL selective bisecondary bond rupturing occurs. Mechanistic pathways of bond-shift and hydrocracking reactions involve both 1,3- and 2,4-metallocyclobutane intermediates in the case of magnesia-supported catalysts, while in the case of the Pt/KL catalyst a 1,3-metallocyclobutane intermediate is preferentially formed. Only terminal scission occurs on Pt/KL. The Pd catalyst demonstrates enhanced activity in demethylation. The observed differences in the mechanistic pathways are explained on the basis of the specific properties of the metal and support. 64 refs., 14 figs., 6 tabs.« less

Water-gas-shift over metal-free nanocrystalline ceria: An experimental and theoretical study

DOE PAGES

Guild, Curtis J.; Vovchok, Dimitriy; Kriz, David A.; ...

2017-01-23

A tandem experimental and theoretical investigation of a mesoporous ceria catalyst reveals the properties of the metal oxide are conducive for activity typically ascribed to metals, suggesting reduced Ce 3+ and oxygen vacancies are responsible for the inherent bi-functionality of CO oxidation and dissociation of water required for facilitating the production of H 2. The degree of reduction of the ceria, specifically the (1 0 0) face, is found to significantly influence the binding of reagents, suggesting reduced surfaces harbor the necessary reactive sites. The metal-free catalysis of the reaction is significant for catalyst design considerations, and the suite ofmore » in situ analyses provides a comprehensive study of the dynamic nature of the high surface area catalyst system. Finally, this study postulates feasible improvements in catalytic activity may redirect the purpose of the water-gas shift reaction from CO purification to primary hydrogen production.« less

Water-gas-shift over metal-free nanocrystalline ceria: An experimental and theoretical study

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

Guild, Curtis J.; Vovchok, Dimitriy; Kriz, David A.

A tandem experimental and theoretical investigation of a mesoporous ceria catalyst reveals the properties of the metal oxide are conducive for activity typically ascribed to metals, suggesting reduced Ce 3+ and oxygen vacancies are responsible for the inherent bi-functionality of CO oxidation and dissociation of water required for facilitating the production of H 2. The degree of reduction of the ceria, specifically the (1 0 0) face, is found to significantly influence the binding of reagents, suggesting reduced surfaces harbor the necessary reactive sites. The metal-free catalysis of the reaction is significant for catalyst design considerations, and the suite ofmore » in situ analyses provides a comprehensive study of the dynamic nature of the high surface area catalyst system. Finally, this study postulates feasible improvements in catalytic activity may redirect the purpose of the water-gas shift reaction from CO purification to primary hydrogen production.« less

Atomic-layered Au clusters on α-MoC as catalysts for the low-temperature water-gas shift reaction

DOE PAGES

Yao, Siyu; Zhang, Xiao; Zhou, Wu; ...

2017-06-22

Here, the water-gas shift (WGS) reaction (where carbon monoxide plus water yields dihydrogen and carbon dioxide) is an essential process for hydrogen generation and carbon monoxide removal in various energy-related chemical operations. This equilibrium-limited reaction is favored at a low working temperature. Potential application in fuel cells also requires a WGS catalyst to be highly active, stable, and energy-efficient and to match the working temperature of on-site hydrogen generation and consumption units. We synthesized layered gold (Au) clusters on a molybdenum carbide (α-MoC) substrate to create an interfacial catalyst system for the ultralow-temperature WGS reaction. Water was activated over α-MoCmore » at 303 kelvin, whereas carbon monoxide adsorbed on adjacent Au sites was apt to react with surface hydroxyl groups formed from water splitting, leading to a high WGS activity at low temperatures.« less

Hindered diffusion of coal liquids. Quarterly report No. 12, June 18, 1995--September 17, 1995

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

Tsotsis, T.T.; Sahimi, M.; Webster, I.A.

1995-12-31

The design of industrial catalysts requires that the diffusivity of the reacting species within the catalyst be accurately known. Nowhere is this more important than in the area of coal liquefaction and upgrading of coal liquids. In this area one is faced with the task of processing a number of heavy oils, containing metals and other contaminants, in a variety of process dependent solvents. It is important, therefore, on the basis of predicting catalyst activity, selectivity, and optimizing reactor performance, that the diffusivities of these oil species be accurately known. It is the purpose of the project described here tomore » provide such a correct concept of coal asphaltenes by careful and detailed investigations of asphaltene transport through porous systems under realistic process temperature and pressure conditions. The experimental studies will be coupled with detailed, in-depth statistical and molecular dynamics models intended to provide a fundamental understanding of the overall transport mechanisms.« less

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.

Cumulative effect of transition metals on nitrogen and fluorine co-doped graphite nanofibers: an efficient and highly durable non-precious metal catalyst for the oxygen reduction reaction.

PubMed

Peera, S Gouse; Arunchander, A; Sahu, A K

2016-08-14

Nitrogen and fluorine co-doped graphite nanofibers (N/F-GNF) and their cumulative effect with Fe and Co have been developed as an alternative non-precious metal catalyst for efficient oxygen reduction reaction (ORR) in acidic media. The synergistic effect between the doped hetero atoms and the co-ordinated Fe and Co towards ORR activity and durability of the catalyst is deeply investigated. A high ORR onset potential comparable with commercial Pt/C catalyst is observed with the Fe-Co/NF-GNF catalyst, which indicates that this catalyst is a potential alternative to Pt/C. A fivefold increase in mass activity is achieved by the Fe-Co/NF-GNF catalyst compared to the simple N/F-GNF catalyst, which endorses the significant role of transition metal atoms in enhancing ORR activity. The advanced Fe-Co/NF-GNF catalyst also exhibits complete tolerance to CH3OH and CO. The Fe-Co/NF-GNF catalyst also exhibits excellent durability towards the ORR with only a 10 mV negative shift in its half wave potential after a 10 000 repeated potential cycling test, whereas in the case of a commercial Pt/C catalyst there was an ∼110 mV negative shift under similar environmental conditions. More stringent corrosive test cycles were also performed by maintaining the cell as high as 1.4 V with a later decrease to 0.6 V vs. RHE for 300 cycles, which showed the excellent durability of the Fe-Co/NF-GNF catalyst in comparison with the Pt/C catalyst. XPS analysis of the Fe-Co/NF-GNF catalyst presents the ORR active chemical states of N (pyridinic-N and graphitic-N) and F (semi-ionic-F) and the co-ordinated sites of Fe and Co species with the dopants. The excellent performance and durability of the Fe-Co/NF-GNF catalyst is due to the synergistic effect between the hetero atoms dopants (N and F) and strong co-ordinating bonds of M-N-C, which protect the graphene layers around the metallic species and greatly mitigates the leaching of Co and Fe during the long term cycling test. The high activity and long term durability of the Fe-Co/NF-GNF catalyst make it a promising ORR electrocatalyst for the fuel cell cathode reaction.

Poisoning of a silica supported cobalt catalyst due to the presence of sulfur impurities in syngas during Fischer-Tropsch synthesis: Effect of chelating agent

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

Bambal, A.S.; Gardner, T.H.; Kugler, E.L.

2012-01-01

Sulfur compounds that are generally found in syngas derived from coal and biomass are a poison to Fischer-Tropsch (FT) catalysts. The presence of sulfur impurities in the ppm range can limit the life of a FT catalyst to a few hours or a few days. In this study, FT synthesis was carried out in a fixed-bed reactor at 230 °C, 20 bar, and 13,500 Ncm3/h/gcat for 72 h using syngas with H2/CO = 2.0. Cobalt-based catalysts were subjected to poisoning by 10 and 50 ppm sulfur in the syngas. The performance of FT catalyst was compared in context of syngasmore » conversion, product selectivities and yields, during the poisoning as well as post-poisoning stages. At both the impurity concentrations, the sulfur was noted to cause permanent loss in the activity, possibly by adsorbing irreversibly on the surface. The sulfur poison affects the hydrogenation and the chain-propagation ability of the catalysts, and shifts the product selectivity towards short-chain hydrocarbons with higher percentages of olefins. Additional diffusion limitations caused due to sulfur poisoning are thought to alter the product selectivity. The shifts in product selectivities suggest that the sulfur decreases the ability of the catalyst to form C-C bonds to produce longer-chain hydrocarbons. The selective blocking of sulfur is thought to affect the hydrogenation ability on the catalyst, resulting in more olefins in the product after sulfur poisoning. The sulfur poisoning on the cobalt catalyst is expected to cause an increase in the number of sites responsible for WGS or to influence the Boudouard reaction, resulting in a higher CO2 selectivity. Both the sites responsible for CO adsorptions as well as the sites for chain growth are poisoned during the poisoning. Additionally, the performance of a base-case cobalt catalyst is compared with that of catalysts modified by chelating agents (CAs). The superior performance of CA-modified catalysts during sulfur poisoning is attributed to the presence of smaller crystallite sizes and higher dispersions of cobalt on the support. Finally, the sulfur deactivation data is modeled by a simple kinetic expression to determine the deactivation constant, deactivation rates and half-life of the FT catalyst.« less

Department of Defense Financial Management Regulation. Volume 8. Civilian Pay Policy Procedures

DTIC Science & Technology

1999-08-01

servicing HRO perform a review of employee records to ensure that previously reported retirement plans are correct. Ensure that frozen CSRS accounts... meal periods) occur during the hours specified. See 53 Comp. Gen. 814 (1974) (reference (p)). Shift differential also is payable when an employee is: 1...Temporary Quarters Subsistence Allowance. The TQSA is an allowance granted to an employee for the reasonable cost of temporary quarters, meals and laundry

Highly stable CuO incorporated TiO(2) catalyst for photo-catalytic hydrogen production from H(2)O.

PubMed

Bandara, J; Udawatta, C P K; Rajapakse, C S K

2005-11-01

A CuO incorporated TiO(2) catalyst was found to be an active photo-catalyst for the reduction of H(2)O under sacrificial conditions. The catalytic activity originates from the photogeneration of excited electrons in the conduction bands of both TiO(2) and CuO resulting in a build-up of excess electrons in the conduction band of CuO. Consequently, the accumulation of excess electrons in CuO causes a negative shift in the Fermi level of CuO. The efficient inter-particle charge transfer leads to a higher catalytic activity and the formation of highly reduced states of TiO(2)/CuO, which are stable even under oxygen saturated condition. Negative shift in the Fermi level of CuO of the catalyst TiO(2)/CuO gains the required over-voltage necessary for efficient water reduction reaction. The function of CuO is to help the charge separation and to act as a water reduction site. The amount of CuO and crystalline structure were found to be crucial for the catalytic activity and the optimum CuO loading was ca. approximately 5-10%(w/w).

Development of a ruthenium/phosphite catalyst system for domino hydroformylation-reduction of olefins with carbon dioxide.

PubMed

Liu, Qiang; Wu, Lipeng; Fleischer, Ivana; Selent, Detlef; Franke, Robert; Jackstell, Ralf; Beller, Matthias

2014-06-02

An efficient domino ruthenium-catalyzed reverse water-gas-shift (RWGS)-hydroformylation-reduction reaction of olefins to alcohols is reported. Key to success is the use of specific bulky phosphite ligands and triruthenium dodecacarbonyl as the catalyst. Compared to the known ruthenium/chloride system, the new catalyst allows for a more efficient hydrohydroxymethylation of terminal and internal olefins with carbon dioxide at lower temperature. Unwanted hydrogenation of the substrate is prevented. Preliminary mechanism investigations uncovered the homogeneous nature of the active catalyst and the influence of the ligand and additive in individual steps of the reaction sequence. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Shape-Shifting Neoliberalism and World Bank Education Policy: A Response to Steven Klees

ERIC Educational Resources Information Center

Bergeron, Suzanne

2008-01-01

In his article titled "A Quarter Century of Neoliberal Thinking in Education: Misleading Analyses and Failed Policies", Steven J. Klees provides a rich account of how educational policy has been influenced by a shift towards neoliberal economic thinking since the 1980s. He also effectively demonstrates the negative impact of this experiment in…

Shifting Educational Paradigms: From Traditional to Competency-Based Education for Diverse Learners

ERIC Educational Resources Information Center

Sullivan, Susan C.; Downey, Jayne A.

2015-01-01

In pursuit of innovative educational opportunities, district administration piloted competency-based education in their alternative program. This qualitative study used semi-structured interviews with school personnel to document perspectives of the programmatic shift. Analyses found local and national mandates, a catalyst, and a common moral…

Temporal dynamics of the circadian heart rate following low and high volume exercise training in sedentary male subjects.

PubMed

Jelinek, Herbert F; Karmakar, C; Kiviniemi, A M; Hautala, A J; Tulppo, M P; Mäkikallio, T H; Huikuri, H V; Khandoker, A H; Palaniswami, M

2015-10-01

Increased risk of arrhythmic events occurs at certain times during the circadian cycle with the highest risk being in the second and fourth quarter of the day. Exercise improves treatment outcome in individuals with cardiovascular disease. How different exercise protocols affect the circadian rhythm and the associated decrease in adverse cardiovascular risk over the circadian cycle has not been shown. Fifty sedentary male participants were randomized into an 8-week high volume and moderate volume training and a control group. Heart rate was recorded using Polar Electronics and investigated with Cosinor analysis and by Poincaré plot derived features of SD1, SD2 and the complex correlation measure (CCM) at 1-h intervals over the 24-h period. Moderate exercise significantly increased vagal modulation and the temporal dynamics of the heart rate in the second quarter of the circadian cycle (p = 0.004 and p = 0.007 respectively). High volume exercise had a similar effect on vagal output (p = 0.003) and temporal dynamics (p = 0.003). Cosinor analysis confirms that the circadian heart rate displays a shift in the acrophage following moderate and high volume exercise from before waking (1st quarter) to after waking (2nd quarter of day). Our results suggest that exercise shifts vagal influence and increases temporal dynamics of the heart rate to the 2nd quarter of the day and suggest that this may be the underlying physiological change leading to a decrease in adverse arrhythmic events during this otherwise high-risk period.

Kinetics of oxygen-enhanced water gas shift on bimetallic catalysts and the roles of metals and support

NASA Astrophysics Data System (ADS)

Kugai, Junichiro

The post-processing of reformate is an important step in producing hydrogen (H2) with low carbon monoxide (CO) for low temperature fuel cells from syn-gas. However, the conventional process consists of three steps, i.e. two steps of water gas shift (WGS) and preferential oxidation (PROX) of CO, and it is not suitable for mobile applications due to the large volume of water gas shift (WGS) catalysts and conditioning and/or regeneration necessary for these catalysts. Aiming at replacing those three steps by a simple one-step process, small amount of oxygen was added to WGS (the reaction called oxygen-enhanced water gas shift or OWGS) to promote the reaction kinetics and low pyrophoric ceria-supported bimetallic catalysts were employed for stable performance in this reaction. Not only CO conversion, but also H2 yield was found to increase by the O2 addition on CeO2-supported catalysts. The characteristics of OWGS, high H2 production rate at 200 to 300°C at short contact time where unreacted O2 exists, evidenced the impact of O2 addition on surface species on the catalyst. Around 1.5 of reaction order in CO for various CeO2-supported metal catalysts for OWGS compared to reaction orders in CO ranging from -0.1 to 0.6 depending on metal species for WGS shows O2 addition decreases CO coverage to free up the active sites for co-reactant (H2O) adsorption and activation. Among the monometallic and bimetallic catalysts, Pt-Cu and Pd-Cu bimetallic catalysts were superior to monometallic catalysts in OWGS. These bimetallic components were found to form alloys where noble metal is surrounded mainly by Cu to have strong interaction between noble metal and copper resulting in high OWGS activity and low pyrophoric property. The metal loadings were optimized for CeO2-supported Pd-Cu bimetallic system and 2 wt% Pd with 5 -- 10 wt% Cu were found to be the optimum for the present OWGS condition. In the kinetic study, Pd in Pd-Cu was shown to increase the active sites for H2O dissociation and/or the subsequent reaction with chemisorbed CO as well as Pd keeps Cu in reduced state. Cu was found to keep Pd dispersed, suppress H2 activation on Pd, and facilitate CO 2 desorption from catalyst surface. While composition and structure of metal have large impacts on OWGS performance, CeO2 was shown to create new sites for H2O activation at metal-ceria interfacial region in concert with metal. These new sites strongly activate H2O to drive OWGS and WGS compared to the pure metallic sites which are present in majority on Al2O3-supported catalyst. The observed two regimes of turnover rate, the one dependent on catalyst surface area and the other independent of surface area, strongly suggested bifunctional reaction pathway where the reaction rate is determined by activation of H2O and by association of chemisorbed CO and H 2O. The associative route was also evidenced by pulse response study where the reaction occurs only when CO and H2O pulses are supplied together, and thus pre-adsorbed species such as formate and carbonate identified by FT-IR are proven to be spectators. No correlation between WGS rate and isotopic exchange rate of molecularly adsorbed D2O with H 2 showed H2O dissociation is necessary for WGS to occur. Long duration tests revealed CeO2-supported Pd-Cu, Pt-Cu and Cu catalysts are stable in OWGS condition compared to Pt, Pd, and Al 2O3-supported Pd-Cu catalysts which exhibited continuous deactivation during about 70 hours of test. The addition of Cu prevents agglomeration of monometallic Pd and carbonate formation on monometallic Pt during the reaction. The better activity and stability of Pd-Cu and Pt-Cu bimetallic catalysts in the realistic OWGS condition were ascribed to the unique active sites consisting of highly dispersed Pd in Cu or Pt in Cu on CeO2, which are good for H2O activation with low reaction inhibition by the product gases. Pt monometallic catalyst showed and highest activity in OWGS in the absence of product gases, but this was found vulnerable in the presence of product gases due to strong adsorption of H2 and CO2 on this catalyst. (Abstract shortened by UMI.)

Atomic level study of water-gas shift catalysts via transmission electron microscopy and x-ray spectroscopy

NASA Astrophysics Data System (ADS)

Akatay, Mehmed Cem

Water-gas shift (WGS), CO + H2O ⇆ CO2 + H2 (DeltaH° = -41 kJ mol -1), is an industrially important reaction for the production of high purity hydrogen. Commercial Cu/ZnO/Al2O3 catalysts are employed to accelerate this reaction, yet these catalysts suffer from certain drawbacks, including costly regeneration processes and sulfur poisoning. Extensive research is focused on developing new catalysts to replace the current technology. Supported noble metals stand out as promising candidates, yet comprise intricate nanostructures complicating the understanding of their working mechanism. In this study, the structure of the supported Pt catalysts is explored by transmission electron microscopy and X-ray spectroscopy. The effect of the supporting phase and the use of secondary metals on the reaction kinetics is investigated. Structural heterogeneities are quantified and correlated with the kinetic descriptors of the catalysts to develop a fundamental understanding of the catalytic mechanism. The effect of the reaction environment on catalyst structure is examined by in-situ techniques. This study benefitted greatly from the use of model catalysts that provide a convenient medium for the atomic level characterization of nanostructures. Based on these studies, Pt supported on iron oxide nano islands deposited on inert spherical alumina exhibited 48 times higher WGS turnover rate (normalized by the total Pt surface area) than Pt supported on bulk iron oxide. The rate of aqueous phase glycerol reforming reaction of Pt supported on multiwall carbon nanotubes (MWCNT) is promoted by co-impregnating with cobalt. The synthesis resulted in a variety of nanostructures among which Pt-Co bimetallic nanoparticles are found to be responsible for the observed promotion. The unprecedented WGS rate of Pt supported on Mo2C is explored by forming Mo 2C patches on top of MWCNTs and the rate promotion is found to be caused by the Pt-Mo bimetallic entities.

Fuel processing for PEM fuel cells: transport and kinetic issues of system design

NASA Astrophysics Data System (ADS)

Zalc, J. M.; Löffler, D. G.

In light of the distribution and storage issues associated with hydrogen, efficient on-board fuel processing will be a significant factor in the implementation of PEM fuel cells for automotive applications. Here, we apply basic chemical engineering principles to gain insight into the factors that limit performance in each component of a fuel processor. A system consisting of a plate reactor steam reformer, water-gas shift unit, and preferential oxidation reactor is used as a case study. It is found that for a steam reformer based on catalyst-coated foils, mass transfer from the bulk gas to the catalyst surface is the limiting process. The water-gas shift reactor is expected to be the largest component of the fuel processor and is limited by intrinsic catalyst activity, while a successful preferential oxidation unit depends on strict temperature control in order to minimize parasitic hydrogen oxidation. This stepwise approach of sequentially eliminating rate-limiting processes can be used to identify possible means of performance enhancement in a broad range of applications.

Studies of Hydrogen Production by the Water Gas Shift Reaction and Related Chemistry

DTIC Science & Technology

1983-04-15

HYDROGEN PRODUCTION BY THE WATER GAS SHIFT REACTION AND RELATED CHEMISTRY Institution: The University of Rochester Department of Chemistry -. Rochester...been in siated for the catalysis of the water gas shift reaction, W20 + CO H𔃼 + C02, and for electrocatalytic oxidation of CO, CO + H󈧘 C02 + 2H...particular interest in adopting water gas shift catalysts to act as electrocatalysts for the anode reaction of CO fuel cells. Under these conditions the best

Effect of steam during Fischer–Tropsch Synthesis using biomass-derived syngas

Treesearch

Zi Wang; Khiet Mai; Nitin Kumar; Thomas Elder; Leslie H. Groom; James J. Spivey

2017-01-01

Fischer–Tropsch synthesis (FTS) with biomass- derived syngas was performed using both iron-based 100Fe/6Cu/4K/25Al catalyst and ruthenium-based 5 % Ru/SiO2 catalyst. During FTS, different concentrations of steam were co-fed with the biomass-derived syngas to promote the water gas shift reaction and increase the H2/ CO ratio...

Investigation of TiO2 based Mixed-metal Oxide Catalysts for the Production of Hydrogen

NASA Astrophysics Data System (ADS)

Luo, Si

Abstract of the Dissertation. Investigation of TiO2 based Mixed-metal Oxide Catalysts for the Production of Hydrogen. by. Si Luo. Doctor of Philosophy. in. Chemistry. Stony Brook University. 2017. The environmental impacts of fossil fuel consumption and the resulting global warming have attracted increasing attention to technologies and fuels that are both sustainable and renewable in the 21st century. To date, hydrogen has been proposed as an encouraging candidate of the next generation of chemical fuels, which meets all demands for carbon free and efficient chemistries that could be produced from a variety of sources. However, despite tremendous efforts, there is a clear need to develop new catalysts for the production of hydrogen through catalytic processes that are sustainable, such as in the photocatalytic splitting of water (PCS: H2O → H2 + 0.5O2) and the water-gas shift process (WGS: CO + H2O → H2 + CO2). This thesis is primarily motivated by this challenge and has focused on the photochemical and thermal production of H2 by the employment of novel TiO2 based catalysts. TiO2 is one of the most widely studied photocatalysts in all history, due to its relatively high activity, robust stability, safety and low cost. In this thesis, several TiO2-based mixed metal oxide nano catalysts (CeOx-TiO2, Ru-TiO2, Ga-TiO2) have been synthesized with carefully controlled morphology/structure and with inclusion of co-catalysts (Pt). These novel materials were comprehensively characterized to better understand their morphology, crystal structure, and electronic properties in an attempt to unravel phenomena responsible for high catalytic performance for the production of H2 from H2O. We have discovered the importance of low-dimensional metal oxide and interfacial stabilized nano-scaled mixed metal oxides for H2 production, while learning how best to tune such structure to optimize both thermal and photochemical conversion. Optimized structure and/or composition have been identified for TiO2 modified in different ways by another metal oxide (CeOx) or with dopants (Ga, Ru). In addition, we have also studied the water gas shift reaction on several TiO2 supported catalysts, where similar concepts can be applied. Advanced In situ characterization enabled the investigation of the catalyst structure, surface chemical intermediates and active species under reaction conditions. The influence of metal-oxide, oxide-oxide interactions has been further revealed for both the water-gas shift and the photocatalytic splitting of water.

Understanding PGM-free Catalysts by Linking Density Functional Theory Calculations and Structural Analysis: Perspectives and Challenges

DOE PAGES

Gonzales, Ivana; Artyushkova, Kateryna; Atanassov, Plamen

2018-03-13

Here, we discuss perspectives and challenges in applying density functional theory for the calculation of spectroscopic properties of platinum group metal (PGM)-free electrocatalysts for oxygen reduction. More specifically, we discuss recent advances in the density functional theory calculations of core-level shifts in binding energies of N 1s electrons as measured by X-ray photoelectron spectroscopy. The link between the density functional theory calculations, the electrocatalytic performance of the catalysts, and structural analysis using modern spectroscopic techniques is expected to significantly increase our understanding of PGM-free catalysts at the molecular level.

Understanding PGM-free Catalysts by Linking Density Functional Theory Calculations and Structural Analysis: Perspectives and Challenges

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

Gonzales, Ivana; Artyushkova, Kateryna; Atanassov, Plamen

Here, we discuss perspectives and challenges in applying density functional theory for the calculation of spectroscopic properties of platinum group metal (PGM)-free electrocatalysts for oxygen reduction. More specifically, we discuss recent advances in the density functional theory calculations of core-level shifts in binding energies of N 1s electrons as measured by X-ray photoelectron spectroscopy. The link between the density functional theory calculations, the electrocatalytic performance of the catalysts, and structural analysis using modern spectroscopic techniques is expected to significantly increase our understanding of PGM-free catalysts at the molecular level.

Electrochemical oxidation of methanol using dppm-bridged Ru/Pd, Ru/Pt and Ru/Au catalysts.

PubMed

Yang, Ying; McElwee-White, Lisa

2004-08-07

The electrochemical oxidation of methanol was carried out using a series of dppm-bridged Ru/Pd, Ru/Pt and Ru/Au heterobimetallic complexes as catalysts. The major oxidation products were formaldehyde dimethyl acetal (dimethoxymethane, DMM) and methyl formate (MF). The Ru/Pd and Ru/Pt bimetallic catalysts generally afforded lower product ratios of DMM/MF and higher current efficiencies than the Ru/Au catalysts. The Ru/Au bimetallics exhibited product ratios and current efficiencies similar to those obtained from the Ru mononuclear compound CpRu(PPh(3))(2)Cl. Increasing the methanol concentration afforded higher current efficiencies, while the addition of water to the samples shifted the product distribution toward the more highly oxidized product, MF.

The Dependence of CNT Aerogel Synthesis on Sulfur-driven Catalyst Nucleation Processes and a Critical Catalyst Particle Mass Concentration.

PubMed

Hoecker, Christian; Smail, Fiona; Pick, Martin; Weller, Lee; Boies, Adam M

2017-11-06

The floating catalyst chemical vapor deposition (FC-CVD) process permits macro-scale assembly of nanoscale materials, enabling continuous production of carbon nanotube (CNT) aerogels. Despite the intensive research in the field, fundamental uncertainties remain regarding how catalyst particle dynamics within the system influence the CNT aerogel formation, thus limiting effective scale-up. While aerogel formation in FC-CVD reactors requires a catalyst (typically iron, Fe) and a promotor (typically sulfur, S), their synergistic roles are not fully understood. This paper presents a paradigm shift in the understanding of the role of S in the process with new experimental studies identifying that S lowers the nucleation barrier of the catalyst nanoparticles. Furthermore, CNT aerogel formation requires a critical threshold of Fe x C y  > 160 mg/m 3 , but is surprisingly independent of the initial catalyst diameter or number concentration. The robustness of the critical catalyst mass concentration principle is proved further by producing CNTs using alternative catalyst systems; Fe nanoparticles from a plasma spark generator and cobaltocene and nickelocene precursors. This finding provides evidence that low-cost and high throughput CNT aerogel routes may be achieved by decoupled and enhanced catalyst production and control, opening up new possibilities for large-scale CNT synthesis.

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

Jacobs, Gary; Pendyala, Venkat Ramana Rao; Martinelli, Michela

XANES K-edge spectra of potassium promoter in precipitated Fe catalysts were acquired following activation by carburization in CO and as a function of time on-stream during the course of a Fischer–Tropsch synthesis run for a 100Fe:2K catalyst by withdrawing catalysts, sealed in wax product, for analysis. CO-activated and end-of-run spectra of the catalyst were also obtained for a 100Fe:5K catalyst. Peaks representing electronic transitions and multiple scattering were observed and resembled reference spectra for potassium carbonate or potassium formate. The shift in the multiple scattering peak to higher energy was consistent with sintering of potassium promoter during the course ofmore » the reaction test. The catalyst, however, retained its carbidic state, as demonstrated by XANES and EXAFS spectra at the iron K-edge, suggesting that sintering of potassium did not adversely affect the carburization rate, which is important for preventing iron carbides from oxidizing. This method serves as a starting point for developing better understanding of the chemical state and changes in structure occurring with alkali promoter.« less

Hydrogen production from algal biomass via steam gasification.

PubMed

Duman, Gozde; Uddin, Md Azhar; Yanik, Jale

2014-08-01

Algal biomasses were tested as feedstock for steam gasification in a dual-bed microreactor in a two-stage process. Gasification experiments were carried out in absence and presence of catalyst. The catalysts used were 10% Fe₂O₃-90% CeO₂ and red mud (activated and natural forms). Effects of catalysts on tar formation and gasification efficiencies were comparatively investigated. It was observed that the characteristic of algae gasification was dependent on its components and the catalysts used. The main role of the catalyst was reforming of the tar derived from algae pyrolysis, besides enhancing water gas shift reaction. The tar reduction levels were in the range of 80-100% for seaweeds and of 53-70% for microalgae. Fe₂O₃-CeO₂ was found to be the most effective catalyst. The maximum hydrogen yields obtained were 1036 cc/g algae for Fucus serratus, 937 cc/g algae for Laminaria digitata and 413 cc/g algae for Nannochloropsis oculata. Copyright © 2014 Elsevier Ltd. All rights reserved.

Design of slurry bubble column reactors: novel technique for optimum catalyst size selection contractual origin of the invention

DOEpatents

Gamwo, Isaac K [Murrysville, PA; Gidaspow, Dimitri [Northbrook, IL; Jung, Jonghwun [Naperville, IL

2009-11-17

A method for determining optimum catalyst particle size for a gas-solid, liquid-solid, or gas-liquid-solid fluidized bed reactor such as a slurry bubble column reactor (SBCR) for converting synthesis gas into liquid fuels considers the complete granular temperature balance based on the kinetic theory of granular flow, the effect of a volumetric mass transfer coefficient between the liquid and the gas, and the water gas shift reaction. The granular temperature of the catalyst particles representing the kinetic energy of the catalyst particles is measured and the volumetric mass transfer coefficient between the gas and liquid phases is calculated using the granular temperature. Catalyst particle size is varied from 20 .mu.m to 120 .mu.m and a maximum mass transfer coefficient corresponding to optimum liquid hydrocarbon fuel production is determined. Optimum catalyst particle size for maximum methanol production in a SBCR was determined to be in the range of 60-70 .mu.m.

Analysis of scanner data for crop inventories

NASA Technical Reports Server (NTRS)

Horvath, R. (Principal Investigator); Cicone, R. C.; Kauth, R. J.; Malila, W. A.; Pont, W.; Thelen, B.; Sellman, A.

1981-01-01

Accomplishments for a machine-oriented small grains labeler T&E, and for Argentina ground data collection are reported. Features of the small grains labeler include temporal-spectral profiles, which characterize continuous patterns of crop spectral development, and crop calendar shift estimation, which adjusts for planting date differences of fields within a crop type. Corn and soybean classification technology development for area estimation for foreign commodity production forecasting is reported. Presentations supporting quarterly project management reviews and a quarterly technical interchange meeting are also included.

Highly dispersed catalysts for coal liquefaction. Quarterly report No. 9, August 23, 1993--November 22, 1993

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

Hirschon, A.S.; Wilson, R.B.

We analyzed two sets of liquefaction experiments, one involved the liquefaction of Black Thunder Coal with the corresponding recycle vehicle, and the second set of liquefaction runs involved the liquefaction of Argonne North Dakota Lignite. We compared coal conversions of Black Thunder coal and recycle solvent using Fe(CO){sub 5} and carbon monoxide/hydrogen atmospheres and a MolyVanL molybdenum catalyst under a hydrogen atmosphere. We also continued our investigation of the effect of water on the conversions. We found that addition of water seemed to decrease the amount of oils; we determined the effect of water with the recycle solvent alone, (nomore » coal added) under similar conditions, and again produced a decrease in oil yields. FIMS analyses of the hexane and toluene soluble fractions seem to indicate that in the experiment when water was added, a considerable amount of light material remained behind in the toluene layer, suggesting that somehow the addition of water decreased the amount of extracted material, perhaps by increasing the amount of polarity of the product. When the conversion was conducted with the MolyVanL molybdenum catalyst a good quality product in terms of lower viscosity was produced; however, conversions to THF soluble material was not increased. We believe the molybdenum catalyst hydrogenated the recycle vehicle rather than effectively converted the coal. In order to eliminate the effect of solvent we have often conducted experiments in an inert solvent with Argonne coals. We conducted several coal conversions experiments using an Argonne North Dakota lignite. We compared several dispersed Fe catalysts and in addition, a nickel catalyst. We investigated nickel as a catalyst since we believe this metal may be more effective in decarboxylating low rank coals. Consistent with this premise we found that the nickel catalyst gave the highest conversions.« less

Method for generating hydrogen for fuel cells

DOEpatents

Ahmed, Shabbir; Lee, Sheldon H. D.; Carter, John David; Krumpelt, Michael

2004-03-30

A method of producing a H.sub.2 rich gas stream includes supplying an O.sub.2 rich gas, steam, and fuel to an inner reforming zone of a fuel processor that includes a partial oxidation catalyst and a steam reforming catalyst or a combined partial oxidation and stream reforming catalyst. The method also includes contacting the O.sub.2 rich gas, steam, and fuel with the partial oxidation catalyst and the steam reforming catalyst or the combined partial oxidation and stream reforming catalyst in the inner reforming zone to generate a hot reformate stream. The method still further includes cooling the hot reformate stream in a cooling zone to produce a cooled reformate stream. Additionally, the method includes removing sulfur-containing compounds from the cooled reformate stream by contacting the cooled reformate stream with a sulfur removal agent. The method still further includes contacting the cooled reformate stream with a catalyst that converts water and carbon monoxide to carbon dioxide and H.sub.2 in a water-gas-shift zone to produce a final reformate stream in the fuel processor.

Fuel processor and method for generating hydrogen for fuel cells

DOEpatents

Ahmed, Shabbir [Naperville, IL; Lee, Sheldon H. D. [Willowbrook, IL; Carter, John David [Bolingbrook, IL; Krumpelt, Michael [Naperville, IL; Myers, Deborah J [Lisle, IL

2009-07-21

A method of producing a H.sub.2 rich gas stream includes supplying an O.sub.2 rich gas, steam, and fuel to an inner reforming zone of a fuel processor that includes a partial oxidation catalyst and a steam reforming catalyst or a combined partial oxidation and stream reforming catalyst. The method also includes contacting the O.sub.2 rich gas, steam, and fuel with the partial oxidation catalyst and the steam reforming catalyst or the combined partial oxidation and stream reforming catalyst in the inner reforming zone to generate a hot reformate stream. The method still further includes cooling the hot reformate stream in a cooling zone to produce a cooled reformate stream. Additionally, the method includes removing sulfur-containing compounds from the cooled reformate stream by contacting the cooled reformate stream with a sulfur removal agent. The method still further includes contacting the cooled reformate stream with a catalyst that converts water and carbon monoxide to carbon dioxide and H.sub.2 in a water-gas-shift zone to produce a final reformate stream in the fuel processor.

Future Challenges in Heterogeneous Catalysis: Understanding Catalysts under Dynamic Reaction Conditions

PubMed Central

Kalz, Kai F.; Kraehnert, Ralph; Dvoyashkin, Muslim; Dittmeyer, Roland; Gläser, Roger; Krewer, Ulrike; Reuter, Karsten

2016-01-01

Abstract In the future, (electro‐)chemical catalysts will have to be more tolerant towards a varying supply of energy and raw materials. This is mainly due to the fluctuating nature of renewable energies. For example, power‐to‐chemical processes require a shift from steady‐state operation towards operation under dynamic reaction conditions. This brings along a number of demands for the design of both catalysts and reactors, because it is well‐known that the structure of catalysts is very dynamic. However, in‐depth studies of catalysts and catalytic reactors under such transient conditions have only started recently. This requires studies and advances in the fields of 1) operando spectroscopy including time‐resolved methods, 2) theory with predictive quality, 3) kinetic modelling, 4) design of catalysts by appropriate preparation concepts, and 5) novel/modular reactor designs. An intensive exchange between these scientific disciplines will enable a substantial gain of fundamental knowledge which is urgently required. This concept article highlights recent developments, challenges, and future directions for understanding catalysts under dynamic reaction conditions. PMID:28239429

Au and Pt nanoparticle supported catalysts tailored for H-2 production: From models to powder catalysts

DOE PAGES

T. D. Nguyen-Phan; Baber, A. E.; Rodriguez, J. A.; ...

2015-12-10

The use of metal nanoparticles (NPs), including Au and Pt, supported over oxides has been pivotal, and is ever increasing in enabling catalytic reactions which target the production of hydrogen. We review here the most recent works pertaining to the fundamental understanding of the structure, morphology, growth, characterization, and intrinsic phenomenological properties of Au– and Pt– based catalysts that influence the reactivity and selectivity to target hydrogen production. We draw on surface science and theoretical methods of model and powder catalysts using high resolution imaging, spectroscopy, scattering experiments, and theoretical studies. Based on these insights we identify key aspects ofmore » studies of supported metal nanoparticle (NP) catalysts for several reactions. The main focus of this review is on the intersection of catalytic chemistry related to the water-gas shift (WGS), oxygenate steam reforming (OSR), and solarassisted reactions (SAR).« less

Fuel Processing System for a 5kW Methanol Fuel Cell Power Unit.

DTIC Science & Technology

1985-11-27

report documents the development and design of a 5kW neat methanol reformer for phosphoric acid fuel cell power plants . The reformer design was based...VAPORIZATION OF METHANOL ........... 4.3 REFORMING/SHIFT CATALYST BED ......... 2 5.0 COMPONENT TESTING............... 5.1 COMBUSTION TUBE...69 36 Catalyst Bed Temperature Profile Before and After Transient ................. 70 37 Assembly -5kw Neat Methanol Reformer. ......... 72 Page No

Catalyst and Fuel Interactions to Optimize Endothermic Cooling

DTIC Science & Technology

2016-08-30

research , special, group study, etc. 3. DATES COVERED. Indicate the time during which the work was performed and the report was written, e.g., Jun 1997...information from the experimental measurements. In close collaboration with experimental group of Anderson, we completed theoretical studies on the effect...observed shifts. 3. Methane Activation by Controlling s- and d-states in Iron-based Single Site Catalysts In a recent experimental finding Guo et

A combined experimental and computational study of water-gas shift reaction over rod-shaped Ce 0.75 M 0.25O 2 (M=Ti, Zr, and Mn) supported Cu catalysts

DOE PAGES

Ren, Zhibo; Peng, Fei; Chen, Biaohua; ...

2017-11-02

Water-gas shift (WGS) reaction over a series of ceria-based mixed oxides supported Cu catalysts was investigated using a combined experimental and theoretical method. The mixed rod-shaped Ce 0.75M 0.25O 2 (M = Ti 4+, Zr 4+, Mn 4+) solid solutions, which majorly expose the (110) and (100) facets, are synthesized by hydrothermal method and used to prepare supported Cu catalysts. We found that the Cu/Ce0.75Ti 0.25O 2 (Cu-CT) exhibits the highest CO conversion in the temperature range of 150-250 °C among all supported Cu catalysts. This is mainly attributed to (i) good dispersion of Cu; (ii) largest amount of moderatemore » copper oxide; and (iii) strongest Cu-support interaction of Cu-CT. And compared to other mixed metals, periodic density functional theory calculations performed, this work further suggest that the introduction of Ti into CeO 2 not only promotes oxygen vacancy formation and CO adsorption, but also facilitates the carboxyl (COOH) formation at the interface of the Cu cluster and the support, which leads to the enhanced catalytic activity of the Cu-CT toward WGS reaction.« less

Tandem catalysis for the production of alkyl lactates from ketohexoses at moderate temperatures

DOE PAGES

Orazov, Marat; Davis, Mark E.

2015-09-08

Retro-aldol reactions have been implicated as the limiting steps in catalytic routes to convert biomass-derived hexoses and pentoses into valuable C2, C3, and C4 products such as glycolic acid, lactic acid, 2-hydroxy-3-butenoic acid, 2,4-dihydroxybutanoic acid, and alkyl esters thereof. Due to a lack of efficient retro-aldol catalysts, most previous investigations of catalytic pathways involving these reactions were conducted at high temperatures (≥160 °C). Here, we report moderate-temperature (around 100 °C) retro-aldol reactions of various hexoses in aqueous and alcoholic media with catalysts traditionally known for their capacity to catalyze 1,2-intramolecular carbon shift (1,2-CS) reactions of aldoses, i.e., various molybdenum oxidemore » and molybdate species, nickel(II) diamine complexes, alkali-exchanged stannosilicate molecular sieves, and amorphous TiO2–SiO2 coprecipitates. Solid Lewis acid cocatalysts that are known to catalyze 1,2-intramolecular hydride shift (1,2-HS) reactions that enable the formation of α-hydroxy carboxylic acids from tetroses, trioses, and glycolaldehyde, but cannot readily catalyze retro-aldol reactions of hexoses and pentoses at these moderate temperatures, are shown to be compatible with the aforementioned retro-aldol catalysts. The combination of a distinct retro-aldol catalyst with a 1,2-HS catalyst enables lactic acid and alkyl lactate formation from ketohexoses at moderate temperatures (around 100 °C), with yields comparable to best-reported chemocatalytic examples at high temperature conditions (≥160 °C). The use of moderate temperatures enables numerous desirable features such as lower pressure and significantly less catalyst deactivation.« less

Poisoning of a Silica-Supported Cobalt Catalyst due to Presence of Sulfur Impurities in Syngas during Fischer–Tropsch Synthesis: Effects of Chelating Agent

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

Bambal, Ashish S.; Guggilla, Vidya S.; Kugler, Edwin L.

2014-04-09

The effects of sulfur impurities on the performance of cobalt-based Fischer–Tropsch catalysts are evaluated under industrially relevant operating conditions of temperature, pressure, and impurity levels. Chelating agents (CAs) were used to modify the SiO 2 support, and the performances of the CA-modified catalysts are compared with conventional Co/SiO 2 catalysts. For both the Co/SiO 2 and CA-modified catalysts, the presence of sulfur in the inlet syngas results in a notable drop in the CO conversion, an undesired shift in the hydrocarbon selectivity toward short-chain hydrocarbons, more olefins in the products, and lower product yields. In the post-poisoning stage, i.e., aftermore » termination of sulfur introduction in the inlet syngas, the CA-modified catalysts recover activity and selectivity (to some extent at least), whereas such trends are not observed for the base-case, i.e., unmodified Co/SiO 2 catalyst. Finally, the improved performance of the CA-modified catalysts in the presence of sulfur is attributed to higher densities of active sites.« less

Spiraling Light with Magnetic Metamaterial Quarter-Wave Turbines.

PubMed

Zeng, Jinwei; Luk, Ting S; Gao, Jie; Yang, Xiaodong

2017-09-19

Miniaturized quarter-wave plate devices empower spin to orbital angular momentum conversion and vector polarization formation, which serve as bridges connecting conventional optical beam and structured light. Enabling the manipulability of additional dimensions as the complex polarization and phase of light, quarter-wave plate devices are essential for exploring a plethora of applications based on orbital angular momentum or vector polarization, such as optical sensing, holography, and communication. Here we propose and demonstrate the magnetic metamaterial quarter-wave turbines at visible wavelength to produce radially and azimuthally polarized vector vortices from circularly polarized incident beam. The magnetic metamaterials function excellently as quarter-wave plates at single wavelength and maintain the quarter-wave phase retardation in broadband, while the turbine blades consist of multiple polar sections, each of which contains homogeneously oriented magnetic metamaterial gratings near azimuthal or radial directions to effectively convert circular polarization to linear polarization and induce phase shift under Pancharatnum-Berry's phase principle. The perspective concept of multiple polar sections of magnetic metamaterials can extend to other analogous designs in the strongly coupled nanostructures to accomplish many types of light phase-polarization manipulation and structured light conversion in the desired manner.

Palladium complexes with simple iminopyridines as catalysts for polyketone synthesis.

PubMed

Rosar, V; Dedeic, D; Nobile, T; Fini, F; Balducci, G; Alessio, E; Carfagna, C; Milani, B

2016-10-07

Four iminopyridines (N-N') differing in the nature of the substituents on the iminic carbon and on the ortho positions of the aryl ring (H or CH3) on the iminic nitrogen were used for the synthesis of neutral and monocationic palladium(ii) complexes of general formulae [Pd(CH3)Cl(N-N')] and [Pd(CH3)(NCCH3)(N-N')][PF6]. The detailed NMR characterization in solution highlighted that: (i) for both series of complexes, the Pd-CH3 signal is progressively shifted to a lower frequency on increasing the number of methyl groups on the ligand skeleton; (ii) for the neutral derivatives, the chemical shift of the (15)N NMR signals, determined through {(1)H,(15)N}-HMBC spectra, is significantly affected by the coordination to palladium; (iii) the coordination induced shift (CIS) of the nitrogen atom trans to the CH3 ligand is smaller than the other. The structure in the solid state for the neutral derivatives with all the four ligands was solved, pointing out that: (iv) the Pd-C bond distance increases with the basicity of the nitrogen-donor ligand; (v) the Pd-N bond distance correlates well with the CIS value. The combining of the solution and solid state structural features allows stating that: (vi) the Pd-CH3 singlet is a good probe for the electron donor capability of the ligand; (vii) the CIS value might be used as a probe for the strength of the Pd-N bond. All monocationic complexes generated active catalysts for the CO/vinyl arene copolymerization, leading to prevailingly syndiotactic polyketones. The catalyst performances, both in terms of catalyst productivity and polymer molecular weight, correlate well with the precatalyst structural features.

Novel process and catalytic materials for converting CO2 and H2 containing mixtures to liquid fuels and chemicals.

PubMed

Meiri, Nora; Dinburg, Yakov; Amoyal, Meital; Koukouliev, Viatcheslav; Nehemya, Roxana Vidruk; Landau, Miron V; Herskowitz, Moti

2015-01-01

Carbon dioxide and water are renewable and the most abundant feedstocks for the production of chemicals and fungible fuels. However, the current technologies for production of hydrogen from water are not competitive. Therefore, reacting carbon dioxide with hydrogen is not economically viable in the near future. Other alternatives include natural gas, biogas or biomass for the production of carbon dioxide, hydrogen and carbon monoxide mixtures that react to yield chemicals and fungible fuels. The latter process requires a high performance catalyst that enhances the reverse water-gas-shift (RWGS) reaction and Fischer-Tropsch synthesis (FTS) to higher hydrocarbons combined with an optimal reactor system. Important aspects of a novel catalyst, based on a Fe spinel and three-reactor system developed for this purpose published in our recent paper and patent, were investigated in this study. Potassium was found to be a key promoter that improves the reaction rates of the RWGS and FTS and increases the selectivity of higher hydrocarbons while producing mostly olefins. It changed the texture of the catalyst, stabilized the Fe-Al-O spinel, thus preventing decomposition into Fe3O4 and Al2O3. Potassium also increased the content of Fe5C2 while shifting Fe in the oxide and carbide phases to a more reduced state. In addition, it increased the relative exposure of carbide iron on the catalysts surface, the CO2 adsorption and the adsorption strength. A detailed kinetic model of the RWGS, FTS and methanation reactions was developed for the Fe spinel catalyst based on extensive experimental data measured over a range of operating conditions. Significant oligomerization activity of the catalyst was found. Testing the pelletized catalyst with CO2, CO and H2 mixtures over a range of operating conditions demonstrated its high productivity to higher hydrocarbons. The composition of the liquid (C5+) was found to be a function of the potassium content and the composition of the feedstock.

An Integrated Computational and Experimental Approach Toward the Design of Materials for Fuel Cell Systems

DTIC Science & Technology

2012-10-01

13 Based on the limited work done, the best reported ORR chalcogenide electrocatalysts for PEMFC applications can be ranked as follows: MoRuSe... PEMFC catalysts is the durability of the catalyst particles. Particle size distribution tends to shift towards larger particles during the...the design of new materials for applications in PEMFCs . Reference: A more detailed treatment of the topics of this section, Experimental Target 11

Impact of Contaminants Present in Coal-Biomass Derived Synthesis Gas on Water-gas Shift and Fischer-Tropsch Synthesis Catalysts

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

Alptekin, Gokhan

2013-02-15

Co-gasification of biomass and coal in large-scale, Integrated Gasification Combined Cycle (IGCC) plants increases the efficiency and reduces the environmental impact of making synthesis gas ("syngas") that can be used in Coal-Biomass-to-Liquids (CBTL) processes for producing transportation fuels. However, the water-gas shift (WGS) and Fischer-Tropsch synthesis (FTS) catalysts used in these processes may be poisoned by multiple contaminants found in coal-biomass derived syngas; sulfur species, trace toxic metals, halides, nitrogen species, the vapors of alkali metals and their salts (e.g., KCl and NaCl), ammonia, and phosphorous. Thus, it is essential to develop a fundamental understanding of poisoning/inhibition mechanisms before investingmore » in the development of any costly mitigation technologies. We therefore investigated the impact of potential contaminants (H 2S, NH 3, HCN, AsH 3, PH 3, HCl, NaCl, KCl, AS 3, NH 4NO 3, NH 4OH, KNO 3, HBr, HF, and HNO 3) on the performance and lifetime of commercially available and generic (prepared in-house) WGS and FT catalysts.« less

Novel Approaches to the Production of Higher Alcohols From Synthesis Gas. Quarterly report, January 1 - March 31, 1997

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

Roberts, George W

1998-12-11

A modified analytical system was assembled and calibrated, in preparation for a second run with cesium (Cs)-promoted "zinc chromite" catalyst. A new column for the on-line gas chromatography (GC) was purchased for the analysis of various light olefin and paraffin isomers. A run was carried out in the continuous stirred autoclave using the Cs-promoted catalyst. Decahydronaphfialene was used as the slurry liquid. Reaction conditions were 375°C, 2000 psig total pressure, 0.5 H₂/CO ratio, and 5000 sL/Kg (cat.)-hr. Analysis of the data from this run is in progress. A manuscript on the thermal stability of potential slurry liquids was submitted tomore » 'Industrial and Engineering Chemistry Research,' and a paper was presented at the 1997 Spring National Meeting of the American Institute of Chemical Engineers, Houston, Texas.« less

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

Testing commercial sex workers for sexually transmitted infections in Victoria, Australia: an evaluation of the impact of reducing the frequency of testing.

PubMed

Chow, Eric P F; Fehler, Glenda; Chen, Marcus Y; Bradshaw, Catriona S; Denham, Ian; Law, Matthew G; Fairley, Christopher K

2014-01-01

The frequency of testing sex workers for sexually transmitted infections (STIs) in Victoria, Australia, was changed from monthly to quarterly on 6 October 2012. Our aim was to determine the impact of this change to the clients seen at the Melbourne Sexual Health Centre (MHSC). Computerised medical records of all clients attending at MHSC from 7 October 2011 to 7 October 2013 were analysed. Comparing between the monthly and quarterly testing periods, the number of consultations at MSHC with female sex workers (FSW) halved from 6146 to 3453 (p<0.001) and the consultation time spent on FSW reduced by 40.6% (1942 h to 1153 h). More heterosexual men (p<0.001), and women (p<0.001) were seen in the quarterly testing period. The number of STIs diagnosed in the clinic increased from 2243 to 2589 from the monthly to quarterly period, respectively [15.4% increase (p<0.001)]. Up to AU$247,000 was saved on FSW testing after the shift to quarterly testing. The change to STIs screening frequency for sex workers from monthly to quarterly resulted in a 15% increase in STI diagnoses in the clinic and approximate a quarter of a million dollars was diverted from FSW testing to other clients. Overall the change in frequency is likely to have had a beneficial effect on STI control in Victoria.

Effects of K and Pt promoters on the performance of cobalt catalyst supported on CNTs

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

Zabidi, Noor Asmawati Mohd, E-mail: noorasmawati-mzabidi@petronas.com.my; Ali, Sardar, E-mail: alikhan-635@yahoo.com; Subbarao, Duvvuri, E-mail: duvvuri-subbarao@petronas.com.my

2014-10-24

This paper presents a comparative study on the effects of incorporation of potassium (K) and platinum (Pt) as promoters on the physicochemical properties of cobalt catalyst. The catalyst was prepared by a wet impregnation method on a CNTs support. Samples were characterized using transmission electron microscopy (TEM), H{sub 2}-temperature-programmed reduction (TPR) and X-ray photoelectron spectroscopy (XPS) techniques. Fischer-Tropsch Synthesis (FTS) was carried out in a fixed-bed microreactor at 543 K and 1 atm, with H{sub 2}/CO = 2v/v and space velocity, SV of 12 L/g.h for 5 hours. The K-promoted and Pt-promoted Co catalysts have different physicochemical properties and catalytic performances comparedmore » to that of the un-promoted Co catalyst. XPS analysis revealed that K and Pt promoters induced electronic modifications as exhibited by the shifts in the Co binding energies. Incorporation of 0.06 wt% K and 0.06 wt% Pt in Co/CNTs catalyst resulted in an increase in the CO conversion and C{sub 5+} selectivity and a decrease in methane selectivity. Potassium was found to be a better promoter for Co/CNTs catalyst compared to platinum.« less

Effects of K and Pt promoters on the performance of cobalt catalyst supported on CNTs

NASA Astrophysics Data System (ADS)

Zabidi, Noor Asmawati Mohd; Ali, Sardar; Subbarao, Duvvuri

2014-10-01

This paper presents a comparative study on the effects of incorporation of potassium (K) and platinum (Pt) as promoters on the physicochemical properties of cobalt catalyst. The catalyst was prepared by a wet impregnation method on a CNTs support. Samples were characterized using transmission electron microscopy (TEM), H2-temperature-programmed reduction (TPR) and X-ray photoelectron spectroscopy (XPS) techniques. Fischer-Tropsch Synthesis (FTS) was carried out in a fixed-bed microreactor at 543 K and 1 atm, with H2/ CO = 2v / v and space velocity, SV of 12 L/g.h for 5 hours. The K-promoted and Pt-promoted Co catalysts have different physicochemical properties and catalytic performances compared to that of the un-promoted Co catalyst. XPS analysis revealed that K and Pt promoters induced electronic modifications as exhibited by the shifts in the Co binding energies. Incorporation of 0.06 wt% K and 0.06 wt% Pt in Co/CNTs catalyst resulted in an increase in the CO conversion and C5+ selectivity and a decrease in methane selectivity. Potassium was found to be a better promoter for Co/CNTs catalyst compared to platinum.

A new class of Cu/ZnO catalysts derived from zincian georgeite precursors prepared by co-precipitation† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c6sc04130b Click here for additional data file.

PubMed Central

Smith, Paul J.; Kondrat, Simon A.; Chater, Philip A.; Yeo, Benjamin R.; Shaw, Greg M.; Lu, Li; Bartley, Jonathan K.; Taylor, Stuart H.; Spencer, Michael S.; Kiely, Christopher J.; Kelly, Gordon J.; Park, Colin W.

2017-01-01

Zincian georgeite, an amorphous copper–zinc hydroxycarbonate, has been prepared by co-precipitation using acetate salts and ammonium carbonate. Incorporation of zinc into the georgeite phase and mild ageing conditions inhibits crystallisation into zincian malachite or aurichalcite. This zincian georgeite precursor was used to prepare a Cu/ZnO catalyst, which exhibits a superior performance to a zincian malachite derived catalyst for methanol synthesis and the low temperature water–gas shift (LTS) reaction. Furthermore, the enhanced LTS activity and stability in comparison to that of a commercial Cu/ZnO/Al2O3 catalyst, indicates that the addition of alumina as a stabiliser may not be required for the zincian georgeite derived Cu/ZnO catalyst. The enhanced performance is partly attributed to the exclusion of alkali metals from the synthesis procedure, which are known to act as catalyst poisons. The effect of residual sodium on the microstructural properties of the catalyst precursor was investigated further from preparations using sodium carbonate. PMID:28451351

Fischer–Tropsch Synthesis: XANES Spectra of Potassium in Promoted Precipitated Iron Catalysts as a Function of Time On-stream

DOE PAGES

Jacobs, Gary; Pendyala, Venkat Ramana Rao; Martinelli, Michela; ...

2017-06-06

XANES K-edge spectra of potassium promoter in precipitated Fe catalysts were acquired following activation by carburization in CO and as a function of time on-stream during the course of a Fischer–Tropsch synthesis run for a 100Fe:2K catalyst by withdrawing catalysts, sealed in wax product, for analysis. CO-activated and end-of-run spectra of the catalyst were also obtained for a 100Fe:5K catalyst. Peaks representing electronic transitions and multiple scattering were observed and resembled reference spectra for potassium carbonate or potassium formate. The shift in the multiple scattering peak to higher energy was consistent with sintering of potassium promoter during the course ofmore » the reaction test. The catalyst, however, retained its carbidic state, as demonstrated by XANES and EXAFS spectra at the iron K-edge, suggesting that sintering of potassium did not adversely affect the carburization rate, which is important for preventing iron carbides from oxidizing. This method serves as a starting point for developing better understanding of the chemical state and changes in structure occurring with alkali promoter.« less

Demonstration of Selective Catalytic Reduction (SCR) technology for the control of nitrogen oxide (NO{sub x}) emissions from high-sulfur coal-fired boilers: Innovative Clean Coal Technology (ICCT). Quarterly report No. 7, January--March 1992

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

Not Available

1992-05-01

The objective of this project is to demonstrate and evaluate commercially available Selective Catalytic Reduction (SCR) catalysts from US, Japanese and European catalyst suppliers on a high-sulfur US coal-fired boiler. SCR is a post-combustion nitrogen oxide (NO{sub x}) control technology that involves injecting ammonia into the flue gas generated from coal combustion in an electric utility boiler. The flue gas containing ammonia is then passed through a reactor that contains a specialized catalyst. In the presence of the catalyst, the amonia reacts with NO{sub x} to convert it to nitrogen and water vapor. Although SCR is widely practiced in Japanmore » and Europe, there are numerous technical uncertainties associated with applying SCR to US coals. These uncertainties include: (1) potential catalyst deactivation due to poisoning by trace metal species present in US coals that are not present in other fuels. (2) performance of the technology and effects on the balance-of-plant equipment in the presence of high amounts of SO, and SO{sub 3}. (3) performance of a wide variety of SCR catalyst compositions, geometries and methods of manufacture under typical high-sulfur coal-fired utility operating conditions. These uncertainties will be explored by constructing a series of small-scale SCR reactors and simultaneously exposing different SCR catalysts to flue gas derived from the combustion of high sulfur US coal. The demonstration will be performed at Gulf Power Company`s Plant Crist Unit No. 5 (75 MW capacity) near Pensacola, Florida. The project will be funded by the US Department of Energy (DOE), Southern Company Services, Inc. (SCS on behalf of the entire Southern electric system), and the Electric Power Research Institute.« less

Advanced gasifier and water gas shift technologies for low cost coal conversion to high hydrogen syngas

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

Kramer, Andrew Kramer

The Gas Technology Institute (GTI) and team members RTI International (RTI), Coanda Research and Development, and Nexant, are developing and maturing a portfolio of technologies to meet the United States Department of Energy (DOE) goals for lowering the cost of producing high hydrogen syngas from coal for use in carbon capture power and coal-to-liquids/chemicals. This project matured an advanced pilot-scale gasifier, with scalable and commercially traceable components, to readiness for use in a first-of-a-kind commercially-relevant demonstration plant on the scale of 500-1,000 tons per day (TPD). This was accomplished through cold flow simulation of the gasifier quench zone transition regionmore » at Coanda and through an extensive hotfire gasifier test program on highly reactive coal and high ash/high ash fusion temperature coals at GTI. RTI matured an advanced water gas shift process and catalyst to readiness for testing at pilot plant scale through catalyst development and testing, and development of a preliminary design basis for a pilot scale reactor demonstrating the catalyst. A techno-economic analysis was performed by Nexant to assess the potential benefits of the gasifier and catalyst technologies in the context of power production and methanol production. This analysis showed an 18%reduction in cost of power and a 19%reduction in cost of methanol relative to DOE reference baseline cases.« less

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

Yu, Ning; Rahman, Muhammad Mahfuzur; Chen, Jixiang

Steam reforming of simulated bio-oil (ethanol, acetone, phenol, and acetic acid) and phenol has been studied on K-Ni-Cu-Mg-Ce-O/Al 2O 3 composite catalysts. Complementary characterization techniques, such as nitrogen sorption, XRD, H 2-TPR, H 2-TPD, CO-TPD, CO-DRIFTS, and in situ XPS, were used to correlate surface structure and functionality to catalytic performance of potassium (K) doped catalysts. K doping of the Ni-Cu-Mg-Ce-O/Al 2O 3 catalyst created a Ni°/Ni 2+ mixed active phase, which not only enhanced steam reforming activity, but also suppressed the methanation reaction. In addition, K doping changed the surface acid-basic properties of the catalyst, which instead favor themore » gasifcation and water-gas shift reactions. In conclusion, with the combination of these effects, K doping of Ni-Cu-Mg-Ce-O/Al 2O 3 catalysts led to higher C1 yield and much lower methane formation, favoring hydrogen production in steam reforming of both phenol and simulated bio-oil.« less

Plasmonic-Enhanced Catalysis

DTIC Science & Technology

2012-05-30

shifts that cannot be merely explained hydride formation. These unexpected LSPR shifts may be explained by Au/Pd interdiffusion or silicide formation...photocurrent on a chemically modified gold thin film of metal -semiconductor (TiO2) Schottky diodes. • Intrinsic correlation between the hot electron flow...reaction to study catalyst nanoparticles at the single particle level. As hydrogen gas dissociates and intercalates into Pd, Pd changes from a metal to

Methanol from Wood Waste: A Technical and Economic Study.

DTIC Science & Technology

1977-06-01

percent of the gas is converted to methanol , the balance passing as inerts to the boiler. The reaction is as follows: catalyst 2H + CO ’ CH3OH 2 *-3...the boiler. Catalyst life is expected to be 6 years for methanol synthesis and 2 to 3 years for the shift reactor . PLANT SIZE In a chemical processing...percent of methyl alcohol ( methanol ) in gasoline for automotive use. / At a current consumption rate of 110 billion gallons per year (gpy), 11 billion

Niche shifts and the potential distribution of Phenacoccus solenopsis (Hemiptera: Pseudococcidae) under climate change

PubMed Central

Zhao, Wanqing; Zhao, Qing

2017-01-01

The cotton mealybug, Phenacoccus solenopsis Tinsley (Hemiptera: Pseudococcidae), is a serious invasive species that significantly damages plants of approximately 60 families around the world. It is originally from North America and has also been introduced to other continents. Our goals were to create a current and future potential global distribution map for this pest under climate change with MaxEnt software. We tested the hypothesis of niche conservatism for P. solenopsis by comparing its native niche in North America to its invasive niches on other continents using Principal components analyses (PCA) in R. The potentially suitable habitat for P. solenopsis in its native and non-native ranges is presented in the present paper. The results suggested that the mean temperature of the wettest quarter and the mean temperature of the driest quarter are the most important environmental variables determining the potential distribution of P. solenopsis. We found strong evidence for niche shifts in the realized climatic niche of this pest in South America and Australia due to niche unfilling; however, a niche shift in the realized climatic niche of this pest in Eurasian owing to niche expansion. PMID:28700721

Study of Pt-Rh/CeO2-ZrO2-MxOy (M = Y, La)/Al2O3 three-way catalysts

NASA Astrophysics Data System (ADS)

Jiaxiu, Guo; Zhonghua, Shi; Dongdong, Wu; Huaqiang, Yin; Maochu, Gong; Yaoqiang, Chen

2013-05-01

CeO2-ZrO2-MxOy (M = Y; La) mixed oxides, prepared by co-precipitation method and characterized by Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), Raman spectra (RM) and oxygen pulse reaction, were comparatively investigated to elucidate the combinational effects of Y and/or La oxide promoters on the catalytic activity and anti-aging performance of monolithic cordierite honeycomb catalysts with low Pt and Rh content. The catalytic activities, water-gas shift (WGS) and steam reforming reaction (SR) were studied under a simulated gas mixture. The catalysts were also characterized by H2-temperature-programmed reduction (H2-TPR) and O2-temperature-programmed desorption (O2-TPD). The results showed that the prepared CeO2-ZrO2-MxOy oxides have a face-centered cubic fluorite structure and are nanosize. La3+ ions can significantly improve thermal stability and efficiently retard CeO2-ZrO2 crystal sintering and growth. Doped CeO2-ZrO2 with Y3+ and La3+ has 105 and 60 m2/g surface area and 460 and 390 μmol/g OSC before and after aging. The T50 of fresh Pt-Rh/CZYL/LA is 170 °C for CO, 222 °C for C3H8 and 189 °C for NO, and shift to 205, 262 and 228 °C after hydrothermal aging, which are better than those of Pt-Rh/CZY/LA or Pt-Rh/CZL/LA. WGS and SR are relate to the OSC of oxygen storage materials and absorbed oxygen species on the catalyst surface and affect the three-way catalytic activities of catalysts. The reductive property of noble metals and the dissociatively adsorbed O2 on the surface of catalysts are closely related to the catalytic activities.

The effect of ZnO addition on H2O activation over Co/ZrO2 catalysts

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

Davidson, Stephen D.; Sun, Junming; Wang, Yong

The effect of ZnO addition on the dissociation of H2O and subsequent effects on cobalt oxidation state and ethanol reaction pathway were investigated over Co/ZrO2 catalyst during ethanol steam reforming (ESR). Catalyst physical properties were characterized by BET, XRD, and TEM. To characterize the catalysts ability to dissociate H2O, Raman spectroscopy, H2O-TPO, and pulsed H2O oxidation coupled with H2-TPR were used. It was found that the addition of ZnO to cobalt supported on ZrO2 decreased the activity for H2O dissociation, leading to a lower degree of cobalt oxidation. The decreased H2O dissociation was also found to affect the reaction pathway,more » evidenced by a shift in liquid product selectivity away from acetone and towards acetaldehyde.« less

In situ Mössbauer investigation of iron oxide catalyst in water gas shift reaction - Impact of oxyreduction potential and temperature

NASA Astrophysics Data System (ADS)

Cherkezova-Zheleva, Z.; Mitov, I.

2010-03-01

The aim of the study is to obtain the exact state of iron oxide catalyst active phase in reaction conditions, as well as the correlation between the active phase and catalytic properties of iron-containing catalysts. In situ Mössbauer spectroscopy is the major investigation technique. It is established that the change of reaction conditions (temperature and gas reaction mixture) lead to redistribution of the relative weight of spectra components and influence mainly tetrahedrally and octahedrally coordinated cations in Fe3O4 phase. It was concluded, that the active sites of the catalyst in studied reaction are probably pairs of Fe3++Fe2+-(Fe2.5+) ions, i.e. the mixed valance iron ions. The obtained catalytic activity can be explained with combination of the natural thermo-activated and catalytically induced electron exchange and better synchronizing of oxidation and reduction steps of the catalytic reaction.

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.

Attrition Resistant Iron-Based Fischer-Tropsch Catalysts

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

Jothimurugesan, K.; Goodwin, J.G.; Spivey, J.J.

1997-03-26

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. Iron-based (Fe) catalysts are preferred catalysts for F-T when using low CO/H{sub 2} ratio synthesis gases derived from modem coal gasifiers. This is because in addition to reasonable F-T activity, the FT catalysts also possess high water gas shift (WGS) activity. 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, making 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. The objectives of this research are to develop a better understanding of the parameters affecting attrition resistance 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. Catalyst preparations will be based on the use of spray drying and will be scalable using commercially available equipment. The research will employ among other measurements, attrition testing and F-T synthesis, including long duration slurry reactor runs in order to ascertain the degree of success of the various preparations. The goal is to develop an Fe catalyst which can be used in a SBCR having only an internal filter for separation of the catalyst from the liquid product, without sacrificing F-T activity and selectivity.« less

Attrition Resistant Iron-Based Fischer-Tropsch Catalysts.

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

Jothimurugesan, K.; Goodwin, J.S.; Spivey, J.J.

1997-09-22

The Fischer-Tropsch (F-T) reaction provides a way of converting coal-derived synthesis gas (CO and 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. Iron-based (Fe) catalysts are preferred catalysts for F-T when using low CO/H{sub 2} ratio synthesis gases derived from modern coal gasifiers. This is because in addition to reasonable F-T activity, the F-T catalysts also possess high water gas shift (WGS) activity. However, a seriousmore » problem with the use of Fe catalysts in a SBCR is their tendency to undergo attrition. This can cause fouling/plugging of downstream filters and equipment, making 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. The objectives of this research are to develop a better understanding of the parameters affecting attrition resistance 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. Catalyst preparations will be based on the use of spray drying and will be scalable using commercially available equipment. The research will employ among other measurements, attrition testing and F-T synthesis, including long duration slurry reactor runs in order to ascertain the degree of success of the various preparations. The goal is to develop an Fe catalyst which can be used in a SBCR having only an internal filter for separation of the catalyst from the liquid product, without sacrificing F-T activity and selectivity.« less

Fischer-Tropsch Catalyst for Aviation Fuel Production

NASA Technical Reports Server (NTRS)

DeLaRee, Ana B.; Best, Lauren M.; Bradford, Robyn L.; Gonzalez-Arroyo, Richard; Hepp, Aloysius F.

2012-01-01

As the oil supply declines, there is a greater need for cleaner alternative fuels. There will undoubtedly be a shift from crude oil to nonpetroleum sources as a feedstock for aviation (and other transportation) fuels. The Fischer-Tropsch process uses a gas mixture of carbon monoxide and hydrogen which is converted into various liquid hydrocarbons; this versatile gas-to-liquid technology produces a complex product stream of paraffins, olefins, and oxygenated compounds such as alcohols and aldehydes. The Fischer-Tropsch process can produce a cleaner diesel oil fraction with a high cetane number (typically above 70) without any sulfur and aromatic compounds. It is most commonly catalyzed by cobalt supported on alumina, silica, or titania or unsupported alloyed iron powders. Cobalt is typically used more often than iron, in that cobalt is a longer-active catalyst, has lower water-gas shift activity, and lower yield of modified products. Promoters are valuable in improving Fischer-Tropsch catalyst as they can increase cobalt oxide dispersion, enhance the reduction of cobalt oxide to the active metal phase, stabilize a high metal surface area, and improve mechanical properties. Our goal is to build up the specificity of the Fischer-Tropsch catalyst while adding less-costly transition metals as promoters; the more common promoters used in Fischer-Tropsch synthesis are rhenium, platinum, and ruthenium. In this report we will describe our preliminary efforts to design and produce catalyst materials to achieve our goal of preferentially producing C8 to C18 paraffin compounds in the NASA Glenn Research Center Gas-To-Liquid processing plant. Efforts at NASA Glenn Research Center for producing green fuels using non-petroleum feedstocks support both the Sub-sonic Fixed Wing program of Fundamental Aeronautics and the In Situ Resource Utilization program of the Exploration Technology Development and Demonstration program.

Fischer-Tropsch Catalyst for Aviation Fuel Production

NASA Technical Reports Server (NTRS)

deLaRee, Ana B.; Best, Lauren M.; Hepp, Aloysius F.

2011-01-01

As the oil supply declines, there is a greater need for cleaner alternative fuels. There will undoubtedly be a shift from crude oil to non-petroleum sources as a feedstock for aviation (and other transportation) fuels. The Fischer-Tropsch process uses a gas mixture of carbon monoxide and hydrogen which is converted into various liquid hydrocarbons; this versatile gas-to-liquid technology produces a complex product stream of paraffins, olefins, and oxygenated compounds such as alcohols and aldehydes. The Fischer-Tropsch process can produce a cleaner diesel oil fraction with a high cetane number (typically above 70) without any sulfur and aromatic compounds. It is most commonly catalyzed by cobalt supported on alumina, silica, or titania or unsupported alloyed iron powders. Cobalt is typically used more often than iron, in that cobalt is a longer-active catalyst, has lower water-gas shift activity, and lower yield of modified products. Promoters are valuable in improving Fischer-Tropsch catalyst as they can increase cobalt oxide dispersion, enhance the reduction of cobalt oxide to the active metal phase, stabilize a high metal surface area, and improve mechanical properties. Our goal is to build up the specificity of the Fischer-Tropsch catalyst while adding less-costly transition metals as promoters; the more common promoters used in Fischer-Tropsch synthesis are rhenium, platinum, and ruthenium. In this report we will describe our preliminary efforts to design and produce catalyst materials to achieve our goal of preferentially producing C8 to C18 paraffin compounds in the NASA Glenn Research Center Gas-To-Liquid processing plant. Efforts at NASA Glenn Research Center for producing green fuels using non-petroleum feedstocks support both the Sub-sonic Fixed Wing program of Fundamental Aeronautics and the In Situ Resource Utilization program of the Exploration Technology Development and Demonstration program.

Archimedes' principle for characterisation of recombinant whole cell biocatalysts.

PubMed

Schmitt, Steven; Walser, Marcel; Rehmann, Michael; Oesterle, Sabine; Panke, Sven; Held, Martin

2018-02-14

The ability of whole cells to catalyse multistep reactions, often yielding synthetically demanding compounds later used by industrial biotech or pharma, makes them an indispensable tool of synthetic chemistry. The complex reaction network employed by cellular catalysts and the still only moderate predictive power of modelling approaches leaves this tool challenging to engineer. Frequently, large libraries of semi-rationally generated variants are sampled in high-throughput mode in order to then identify improved catalysts. We present a method for space- and time-efficient processing of very large libraries (10 7 ) of recombinant cellular catalysts, in which the phenotypic characterisation and the isolation of positive variants for the entire library is done within one minute in a single, highly parallelized operation. Specifically, product formation in nanolitre-sized cultivation vessels is sensed and translated into the formation of catalase as a reporter protein. Exposure to hydrogen peroxide leads to oxygen gas formation and thus to a density shift of the cultivation vessel. Exploiting Archimedes' principle, this density shift and the resulting upward buoyancy force can be used for batch-wise library sampling. We demonstrate the potential of the method for both, screening and selection protocols, and envision a wide applicability of the system for biosensor-based assays.

Investigation of the characteristics of a compact steam reformer integrated with a water-gas shift reactor

NASA Astrophysics Data System (ADS)

Seo, Yong-Seog; Seo, Dong-Joo; Seo, Yu-Taek; Yoon, Wang-Lai

The objective of this study is to investigate numerically a compact steam methane reforming (SMR) system integrated with a water-gas shift (WGS) reactor. Separate numerical models are established for the combustion part, SMR and WGS reaction bed. The concentration of species at the exits of the SMR and WGS bed, and the temperatures in the WGS bed are in good agreement with the measured data. Heat transfer to the catalyst beds and the catalytic reactions in the SMR and WGS catalyst bed are investigated as a function of the operation parameters. The conversion of methane at the exit of the SMR catalyst bed is calculated to be 87%, and the carbon monoxide concentration at the outlet of the WGS bed is estimated to be 0.45%. The effects of the cooling heat flux at the outside wall of the system and steam-to-carbon (S/C) ratio are also examined. As the cooling heat flux increases, both the methane conversion and carbon monoxide content are reduced in the SMR bed, and the carbon monoxide conversion is improved in the WGS bed. Both methane conversion and carbon dioxide reduction increase with increasing steam-to-carbon ratio.

Dynamics of CrO 3 –Fe 2 O 3 Catalysts during the High-Temperature Water-Gas Shift Reaction: Molecular Structures and Reactivity

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

Keturakis, Christopher J.; Zhu, Minghui; Gibson, Emma K.

2016-06-13

A series of supported CrO 3/Fe 2O 3 catalysts were investigated for the high-temperature water-gas shift (WGS) and reverse-WGS reactions and extensively characterized using in situ and operando IR, Raman, and XAS spectroscopy during the high-temperature WGS/RWGS reactions. The in situ spectroscopy examinations reveal that the initial oxidized catalysts contain surface dioxo (O=) 2Cr 6+O 2 species and a bulk Fe 2O 3 phase containing some Cr 3+ substituted into the iron oxide bulk lattice. Operando spectroscopy studies during the high-temperature WGS/RWGS reactions show that the catalyst transforms during the reaction. The crystalline Fe 2O 3 bulk phase becomes Femore » 3O 4 ,and surface dioxo (O=) 2Cr 6+O 2 species are reduced and mostly dissolve into the iron oxide bulk lattice. Consequently, the chromium–iron oxide catalyst surface is dominated by FeO x sites, but some minor reduced surface chromia sites are also retained. The Fe 3–-xCr xO 4 solid solution stabilizes the iron oxide phase from reducing to metallic Fe0 and imparts an enhanced surface area to the catalyst. Isotopic exchange studies with C 16O 2/H 2 → C 18O 2/H 2 isotopic switch directly show that the RWGS reaction proceeds via the redox mechanism and only O* sites from the surface region of the chromium–iron oxide catalysts are involved in the RWGS reaction. The number of redox O* sites was quantitatively determined with the isotope exchange measurements under appropriate WGS conditions and demonstrated that previous methods have undercounted the number of sites by nearly 1 order of magnitude. The TOF values suggest that only the redox O* sites affiliated with iron oxide are catalytic active sites for WGS/RWGS, though a carbonate oxygen exchange mechanism was demonstrated to exist, and that chromia is only a textural promoter that increases the number of catalytic active sites without any chemical promotion effect.« less

Halloysite-derived nitrogen doped carbon electrocatalysts for anion exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Lu, Yaxiang; Wang, Lianqin; Preuß, Kathrin; Qiao, Mo; Titirici, Maria-Magdalena; Varcoe, John; Cai, Qiong

2017-12-01

Developing the low-cost, highly active carbonaceous materials for oxygen reduction reaction (ORR) catalysts has been a high-priority research direction for durable fuel cells. In this paper, two novel N-doped carbonaceous materials with flaky and rod-like morphology using the natural halloysite as template are obtained from urea nitrogen source as well as glucose (denoted as GU) and furfural (denoted as FU) carbon precursors, respectively, which can be directly applied as metal-free electrocatalysts for ORR in alkaline electrolyte. Importantly, compared with a benchmark Pt/C (20wt%) catalyst, the as-prepared carbon catalysts demonstrate higher retention in diffusion limiting current density (after 3000 cycles) and enhanced methanol tolerances with only 50-60mV negative shift in half-wave potentials. In addition, electrocatalytic activity, durability and methanol tolerant capability of the two N-doped carbon catalysts are systematically evaluated, and the underneath reasons of the outperformance of rod-like catalysts over the flaky are revealed. At last, the produced carbonaceous catalysts are also used as cathodes in the single cell H2/O2 anion exchange membrane fuel cell (AEMFC), in which the rod-like FU delivers a peak power density as high as 703 mW cm-2 (vs. 1106 mW cm-2 with a Pt/C benchmark cathode catalyst).

What Happens to Therapists Who Work with Sex Offenders?

ERIC Educational Resources Information Center

Farrenkopf, Toni

1992-01-01

Surveyed 24 experienced therapists working with sex offenders regarding personal impact of work. Most reported shift in perspective, becoming discouraged about client change. Several adjustment phases were reported. One-quarter experienced burnout. Alternative to burnout was adaptation: lowering of expectations, objective detachment, acceptance of…

Steam reforming of simulated bio-oil on K-Ni-Cu-Mg-Ce-O/Al 2O 3: The effect of K

DOE PAGES

Yu, Ning; Rahman, Muhammad Mahfuzur; Chen, Jixiang; ...

2018-04-10

Steam reforming of simulated bio-oil (ethanol, acetone, phenol, and acetic acid) and phenol has been studied on K-Ni-Cu-Mg-Ce-O/Al 2O 3 composite catalysts. Complementary characterization techniques, such as nitrogen sorption, XRD, H 2-TPR, H 2-TPD, CO-TPD, CO-DRIFTS, and in situ XPS, were used to correlate surface structure and functionality to catalytic performance of potassium (K) doped catalysts. K doping of the Ni-Cu-Mg-Ce-O/Al 2O 3 catalyst created a Ni°/Ni 2+ mixed active phase, which not only enhanced steam reforming activity, but also suppressed the methanation reaction. In addition, K doping changed the surface acid-basic properties of the catalyst, which instead favor themore » gasifcation and water-gas shift reactions. In conclusion, with the combination of these effects, K doping of Ni-Cu-Mg-Ce-O/Al 2O 3 catalysts led to higher C1 yield and much lower methane formation, favoring hydrogen production in steam reforming of both phenol and simulated bio-oil.« less

Steam reforming of simulated bio-oil on K-Ni-Cu-Mg-Ce-O/Al 2O 3: The effect of K

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

Yu, Ning; Rahman, Muhammad Mahfuzur; Chen, Jixiang

Steam reforming of simulated bio-oil (ethanol, acetone, phenol, and acetic acid) and phenol has been studied on K-Ni-Cu-Mg-Ce-O/Al 2O 3 composite catalysts. Complementary characterization techniques, such as nitrogen sorption, XRD, H 2-TPR, H 2-TPD, CO-TPD, CO-DRIFTS, and in situ XPS, were used to correlate surface structure and functionality to catalytic performance of potassium (K) doped catalysts. K doping of the Ni-Cu-Mg-Ce-O/Al 2O 3 catalyst created a Ni°/Ni 2+ mixed active phase, which not only enhanced steam reforming activity, but also suppressed the methanation reaction. In addition, K doping changed the surface acid-basic properties of the catalyst, which instead favor themore » gasifcation and water-gas shift reactions. In conclusion, with the combination of these effects, K doping of Ni-Cu-Mg-Ce-O/Al 2O 3 catalysts led to higher C1 yield and much lower methane formation, favoring hydrogen production in steam reforming of both phenol and simulated bio-oil.« less

Generations Apart: Xers and Boomers in the Officer Corps

DTIC Science & Technology

2000-10-01

in just 10 years. Notice how less than a quarter of Gen X officers (compared with nearly half of Baby Boomer officers) believe work / life balance is...compatible with an Army career. This is a significant attitudinal shift to take place in only 10 years. The shifting emphasis on work / life balance is a...Army career would allow/allows me to maintain the kind of balance I want between my work and personal life. 47.4 % 21.3 % Figure 4. Work / Life Balance of

Active Duty-U.S. Army Noise Induced Hearing Injury Quarterly Surveillance Q3 2007 thru Q4 2009

DTIC Science & Technology

2014-05-11

years (CY) Q3 2007-Q4 2009 shows incident case rates for sensorineural hearing loss (SNHL), significant threshold shift (STS), tinnitus , and Noise-Induced...Prev Med. 2010;38(1S):S71-S77. Humes LE, Jollenbeck LM, Durch JS. Noise and military service: Implications for hearing loss and tinnitus . Washington...threshold shift 79415 NONSPECIFIC ABNORMAL AUDITORY FUNCTION STUDIES TINN Tinnitus 38830 TINNITUS UNSPECIFIED TINN Tinnitus 38831 SUBJECTIVE TINNITUS

Broadband one-dimensional photonic crystal wave plate containing single-negative materials.

PubMed

Chen, Yihang

2010-09-13

The properties of the phase shift of wave reflected from one-dimensional photonic crystals consisting of periodic layers of single-negative (permittivity- or permeability-negative) materials are demonstrated. As the incident angle increases, the reflection phase shift of TE wave decreases, while that of TM wave increases. The phase shifts of both polarized waves vary smoothly as the frequency changes across the photonic crystal stop band. Consequently, the difference between the phase shift of TE and that of TM wave could remain constant in a rather wide frequency range inside the stop band. These properties are useful to design wave plate or retarder which can be used in wide spectral band. In addition, a broadband photonic crystal quarter-wave plate is proposed.

Alloy catalysts with monolith supports for methanation of coal-derived gases. Quarterly technical progress report, September 21-December 20, 1979

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

Bartholomew, C.H.

1980-01-05

Tests for catalyst deactivation by carbon deposition in a Berty reactor showed that CO partial pressure exerted a greater influence on deactivation than H/sub 2/ partial pressure. In kinetic studies in which H/sub 2/O vapor was added to the reactant gases, H/sub 2/O was found to inhibit the methanation reaction. H/sub 2/O inhibition was found to increase with temperature and loss of activity was observed at H/sub 2/O/CO ratios greater than one. The order of methanation with respect to H/sub 2/ and CO varies over the range of temperature from 498 to 598/sup 0/K. Rate data indicate a change inmore » mechanism or rate determining step at higher temperatures. Our experience with a quartz CFSTR has shown that this reactor is very delicate and needs near constant attention to maintain proper working order.« less

Attrition resistant fluidizable reforming catalyst

DOEpatents

Parent, Yves O [Golden, CO; Magrini, Kim [Golden, CO; Landin, Steven M [Conifer, CO; Ritland, Marcus A [Palm Beach Shores, FL

2011-03-29

A method of preparing a steam reforming catalyst characterized by improved resistance to attrition loss when used for cracking, reforming, water gas shift and gasification reactions on feedstock in a fluidized bed reactor, comprising: fabricating the ceramic support particle, coating a ceramic support by adding an aqueous solution of a precursor salt of a metal selected from the group consisting of Ni, Pt, Pd, Ru, Rh, Cr, Co, Mn, Mg, K, La and Fe and mixtures thereof to the ceramic support and calcining the coated ceramic in air to convert the metal salts to metal oxides.

Wildland fire emissions, carbon, and climate: Seeing the forest and the trees - A cross-scale assessment of wildfire and carbon dynamics in fire-prone, forested ecosystems

Treesearch

Rachel A. Loehman; Elizabeth Reinhardt; Karin L. Riley

2014-01-01

Wildfires are an important component of the terrestrial carbon cycle and one of the main pathways for movement of carbon from the land surface to the atmosphere. Fires have received much attention in recent years as potential catalysts for shifting landscapes from carbon sinks to carbon sources. Unless structural or functional ecosystem shifts occur, net carbon balance...

Structural and surface properties of CuO-ZnO-Cr{sub 2}O{sub 3} catalysts and their relationship with selectivity to higher alcohol synthesis

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

Campos-Martin, J.M.; Fierro, J.L.G.; Guerrero-Ruiz, A.

1995-10-01

A series of copper-zinc-chromium catalysts of different compositions and calcination temperatures has been prepared, characterized by several techniques (BET specific surface area, XRD, gravimetric TPR, TPD-CO, and XPS), and tested under high alcohol synthesis (HAS) conditions. CO hydrogenation was carried out at reaction temperatures of 523-598 K and 50 bar total pressure. The influence of catalyst composition, calcination temperature, and surface characteristics on the HAS selectivity was studied. The optimum HAS yields were found in the low Cr content region, but chromium was needed. Although chromium oxide does not seem to be involved in the catalytic site, its presence inmore » the catalyst composition is essential, owing to the larger specific surfaces and catalyst stability obtained at the highest reaction temperatures. For low Cr content composition, the temperature-programmed reduction (TPR) profiles were shifted to higher temperatures and simultaneously larger CO{sub 2} amounts were found in the temperature-programmed desorption profiles of adsorbed CO (TPD-CO). Photoelectron spectra (XPS) revealed that the oxidation state of copper is Cu{sup 2+} in the calcined catalysts and Cu{sup O} in the reduced ones; Cu{sup +} was only stabilized in a CuCr{sub 2}O{sub 4} spinel in the Cr-rich catalysts. These features derived from catalyst characterization are discussed in the framework of the catalytic behaviour for HAS synthesis. 53 refs., 7 figs., 4 tabs.« less

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

Warren, B.K.; Campbell, K.D.

Methane oxidative coupling studies were carried out in an atmospheric quartz reactor at temperatures between 700 and 800/degree/C. New catalysts prepared and studied included doped alkaline earth catalysts, lanthanide oxides, and proprietary catalysts. Neodymium oxide, Nd/sub 2/O/sub 3/, was found to be as active and selective as samarium oxide, Sm/sub 2/O/sub 3/, in contrast to literature reports. Proprietary Union Carbide catalysts (UCC-S:1) showed initial methane conversions and C/sub 2/ selectivities comparable to literature catalysts. Atypically low carbon dioxide to carbon monoxide ratios (typically ten times lower than those seen in the literature or other catalysts tested) and high ethylene tomore » ethane ratios (3 to 6 compared to typical literature ratios below 1) were obtained. These results are interesting because ethylene is more valuable than ethane and carbon monoxide is more valuable than carbon dioxide. With these UCC-S:1 catalysts, rapid deactivation was coupled with an observed shift in product ratios toward those more typical in the literature. Initial cases for process conceptualization studies were selected. The Comparison Case will consist of the conversion sequence from methane to synthesis gas to methanol to olefins to liquid hydrocarbon fuels. Case 1 will consist of the conversion of methane to ethylene and ethane. Case 2 will be the direct conversion of methane to C/sub 2/'s followed by conversion to liquid hydrocarbon fuels. 7 figs., 18 tabs.« less

[Effect of the introduction of "on demand" nursing shifts on hours of absenteeism].

PubMed

Blanca Gutiérrez, Joaquín Jesús; del Rosal González, Antonio; González Ábalos, María de Los Ángeles; Aceituno Herrera, Ana; Martín Afán de Rivera, Juan Carlos; Arjona González, Ana

2012-01-01

The objective of this study was to analyze the effect of the introduction of a new system of rotating shifts on nursing absenteeism. The novelty of this system is that both the time distribution and the planning and allocation of shifts is carried out according to the wishes of the participating nurses. This study was performed in the Infanta Margarita Hospital (Cordoba, Spain) and the new shift system was introduced in the first quarter of 2011. The total number of absolute hours of absence decreased from 5551 to 3289 per semester. The implementation of this new "on demand" shift system seems to have significantly reduced hours of absence. This strategy aims to reconcile nurses' working hours with their personal and family lives. Copyright © 2011 SESPAS. Published by Elsevier Espana. All rights reserved.

Highly active Au/δ-MoC and Au/β-Mo 2C catalysts for the low-temperature water gas shift reaction: effects of the carbide metal/carbon ratio on the catalyst performance

DOE PAGES

Posada-Pérez, Sergio; Gutiérrez, Ramón A.; Zuo, Zhijun; ...

2017-05-08

In this paper, the water gas shift (WGS) reaction catalyzed by orthorhombic β-Mo 2C and cubic δ-MoC surfaces with and without Au clusters supported thereon has been studied by means of a combination of sophisticated experiments and state-of-the-art computational modeling. Experiments evidence the importance of the metal/carbon ratio on the performance of these systems, where Au/δ-MoC is presented as a suitable catalyst for WGS at low temperatures owing to its high activity, selectivity (only CO 2 and H 2 are detected), and stability (oxycarbides are not observed). Periodic density functional theory-based calculations show that the supported Au clusters and themore » Au/δ-MoC interface do not take part directly in water dissociation but their presence is crucial to switch the reaction mechanism, drastically decreasing the effect of the reverse WGS reaction and favoring the WGS products desorption, thus leading to an increase in CO 2 and H 2 production. Finally, the present results clearly display the importance of the Mo/C ratio and the synergy with the admetal clusters in tuning the activity and selectivity of the carbide substrate.« less

Highly active Au/δ-MoC and Au/β-Mo 2C catalysts for the low-temperature water gas shift reaction: effects of the carbide metal/carbon ratio on the catalyst performance

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

Posada-Pérez, Sergio; Gutiérrez, Ramón A.; Zuo, Zhijun

In this paper, the water gas shift (WGS) reaction catalyzed by orthorhombic β-Mo 2C and cubic δ-MoC surfaces with and without Au clusters supported thereon has been studied by means of a combination of sophisticated experiments and state-of-the-art computational modeling. Experiments evidence the importance of the metal/carbon ratio on the performance of these systems, where Au/δ-MoC is presented as a suitable catalyst for WGS at low temperatures owing to its high activity, selectivity (only CO 2 and H 2 are detected), and stability (oxycarbides are not observed). Periodic density functional theory-based calculations show that the supported Au clusters and themore » Au/δ-MoC interface do not take part directly in water dissociation but their presence is crucial to switch the reaction mechanism, drastically decreasing the effect of the reverse WGS reaction and favoring the WGS products desorption, thus leading to an increase in CO 2 and H 2 production. Finally, the present results clearly display the importance of the Mo/C ratio and the synergy with the admetal clusters in tuning the activity and selectivity of the carbide substrate.« less

Level Alignment as Descriptor for Semiconductor/Catalyst Systems in Water Splitting: The Case of Hematite/Cobalt Hexacyanoferrate Photoanodes.

PubMed

Hegner, Franziska Simone; Cardenas-Morcoso, Drialys; Giménez, Sixto; López, Núria; Galan-Mascaros, Jose Ramon

2017-11-23

The realization of artificial photosynthesis may depend on the efficient integration of photoactive semiconductors and catalysts to promote photoelectrochemical water splitting. Many efforts are currently devoted to the processing of multicomponent anodes and cathodes in the search for appropriate synergy between light absorbers and active catalysts. No single material appears to combine both features. Many experimental parameters are key to achieve the needed synergy between both systems, without clear protocols for success. Herein, we show how computational chemistry can shed some light on this cumbersome problem. DFT calculations are useful to predict adequate energy-level alignment for thermodynamically favored hole transfer. As proof of concept, we experimentally confirmed the limited performance enhancement in hematite photoanodes decorated with cobalt hexacyanoferrate as a competent water-oxidation catalyst. Computational methods describe the misalignment of their energy levels, which is the origin of this mismatch. Photoelectrochemical studies indicate that the catalyst exclusively shifts the hematite surface state to lower potentials, which therefore reduces the onset for water oxidation. Although kinetics will still depend on interface architecture, our simple theoretical approach may identify and predict plausible semiconductor/catalyst combinations, which will speed up experimental work towards promising photoelectrocatalytic systems. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Advanced Catalysts for Fuel Cells

NASA Technical Reports Server (NTRS)

Narayanan, Sekharipuram R.; Whitacre, Jay; Valdez, T. I.

2006-01-01

This viewgraph presentation reviews the development of catalyst for Fuel Cells. The objectives of the project are to reduce the cost of stack components and reduce the amount of precious metal used in fuel cell construction. A rapid combinatorial screening technique based on multi-electrode thin film array has been developed and validated for identifying catalysts for oxygen reduction; focus shifted from methanol oxidation in FY05 to oxygen reduction in FY06. Multi-electrode arrays of thin film catalysts of Pt-Ni and Pt-Ni-Zr have been deposited. Pt-Ni and have been characterized electrochemically and structurally. Pt-Ni-Zr and Pt-Ni films show higher current density and onset potential compared to Pt. Electrocatalytic activity and onset potential are found to be strong function of the lattice constant. Thin film Pt(59)Ni(39)Zr(2) can provide 10 times the current density of thin film Pt. Thin film Pt(59)Ni(39)Zr(2) also shows 65mV higher onset potential than Pt.

Nanosized CuO and ZnO Catalyst Supported on Honeycomb-Typed Monolith for Hydrogenation of Carbon Dioxide to Methyl Alcohol.

PubMed

Park, Chul-Min; Ahn, Won-Ju; Jo, Woong-Kyu; Song, Jin-Hun; Oh, Chang-Yeop; Jeong, Young-Shin; Chung, Min-Chul; Park, Kwon-Pil; Kim, Ki-Joong; Jeong, Woon-Jo; Sohn, Bo-Kyun; Jung, Sang-Chul; Lee, Do-Jin; Ahn, Byeong-Kwon; Ahn, Ho-Geun

2015-01-01

The greenhouse effect of carbon dioxide (CO2) has been recognized as one of the most serious problems in the world. Conversion of CO2 to methyl alcohol (CH3OH) was studied using catalytic chemical methods. Honeycomb-typed monolith used as catalyst support was 400 cell/inch2. Pretreatment of the monolith surface was carried out by thermal treatment and acid treatment. Monolith-supported nanosized CuO-ZnO catalysts were prepared by wash-coat method. The prepared catalysts were characterized by using SEM, TEM, and XRD. The catalytic activity for CO2 hydrogenation to CH3OH was investigated using a flow-type reactor with varying reaction temperature, reaction pressure and contact time. Conversion of CO2 was increased with increasing reaction temperature, but selectivity to CH3OH was decreased. Optimum reaction temperature was about 250 degrees C under 20 atm. Because of the reverse water gas shift reaction.

Saving Chinese-Language Education in Singapore

ERIC Educational Resources Information Center

Lee, Cher Leng

2012-01-01

Three-quarters of Singapore's population consists of ethnic Chinese, and yet, learning Chinese (Mandarin) has been a headache for many Singapore students. Recently, many scholars have argued that the rhetoric of language planning for Mandarin Chinese should be shifted from emphasizing its cultural value to stressing its economic value since…

Selective Deoxygenation of Biomass‐Derived Bio‐oils within Hydrogen‐Modest Environments: A Review and New Insights

PubMed Central

Rogers, Kyle A.

2016-01-01

Abstract Research development of processes for refining bio‐oils is becoming increasingly popular. One issue that these processes possess is their high requirement for H2 gas. In response, researchers must develop catalysts that perform deoxygenation while minimizing H2 consumption—selective deoxygenation. Unlike traditional deoxygenation processes, selective deoxygenation reactions and catalysts represent an information gap that, prior to this publication, has yet to be reviewed. This review addresses the gap by providing both a summary of recent research developments and insight into future developments of new catalytic materials. Bifunctional catalysts containing a combination of oxophilicity and an active metal phase appear to be the most beneficial for selective deoxygenation processes in a H2‐modest environment. It is important that catalysts have a supply of disassociated hydrogen, because without such, activity and stability will suffer. The authors recommend to maximize the use of internally available hydrogen in bio‐fuel, which may be the only viable approach for deoxygenation if external H2 gas is limited. This would be possible through the development of catalysts that promote both the water–gas‐shift and deoxygenation reactions. PMID:27385663

Sensitivity of Fischer-Tropsch Synthesis and Water-Gas Shift Catalysts to Poisons from High-Temperature High-Pressure Entrained-Flow (EF) Oxygen-Blown Gasifier Gasification of Coal/Biomass Mixtures

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

Burtron Davis; Gary Jacobs; Wenping Ma

The successful adaptation of conventional cobalt and iron-based Fischer-Tropsch synthesis catalysts for use in converting biomass-derived syngas hinges in part on understanding their susceptibility to byproducts produced during the biomass gasification process. With the possibility that oil production will peak in the near future, and due to concerns in maintaining energy security, the conversion of biomass-derived syngas and syngas derived from coal/biomass blends to Fischer-Tropsch synthesis products to liquid fuels may provide a sustainable path forward, especially considering if carbon sequestration can be successfully demonstrated. However, one current drawback is that it is unknown whether conventional catalysts based on ironmore » and cobalt will be suitable without proper development because, while ash, sulfur compounds, traces of metals, halide compounds, and nitrogen-containing chemicals will likely be lower in concentration in syngas derived from mixtures of coal and biomass (i.e., using an entrained-flow oxygen-blown gasifier) than solely from coal, other byproducts may be present in higher concentrations. The current project examines the impact of a number of potential byproducts of concern from the gasification of biomass process, including compounds containing alkali chemicals like the chlorides of sodium and potassium. In the second year, researchers from the University of Kentucky Center for Applied Energy Research (UK-CAER) continued the project by evaluating the sensitivity of a commercial iron-chromia high temperature water-gas shift catalyst (WGS) to a number of different compounds, including KHCO{sub 3}, NaHCO{sub 3}, HCl, HBr, HF, H{sub 2}S, NH{sub 3}, and a combination of H{sub 2}S and NH{sub 3}. Cobalt and iron-based Fischer-Tropsch synthesis (FT) catalysts were also subjected to a number of the same compounds in order to evaluate their sensitivities.« 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

Simultaneous weak measurement of angular and spatial Goos-Hänchen and Imbert-Fedorov shifts

NASA Astrophysics Data System (ADS)

Prajapati, Chandravati; Viswanathan, Nirmal K.

2017-10-01

We propose and demonstrate the weak measurement scheme to simultaneously measure the amplified angular and spatial contributions to the Goos-Hänchen (GH) and Imbert-Fedorov (IF) shifts, due to transmission through a glass plate. We have studied two cases of post-selection using a polarizer in the first case and a quarter-wave plate (QWP)-polarizer combination in the second case. The two cases are analyzed theoretically using Jones calculus of polarization formalism and the results are verified experimentally. In the first case of post-selection, the projection of the polarizer at +/- {{Δ }} away from the crossed position amplifies the angular GH and IF shifts, while in the second case of post-selection, the projection of QWP at +/- {{Δ }} and polarizer kept fixed measures the polarization ellipticity in the beam and thus amplifies the spatial shift along with the angular shift simultaneously, for {{Δ }}\\ll 1.

The selective hydrogenation of crotonaldehyde over bimetallic catalysts

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

Schoeb, Ann M.

1997-10-17

The selective hydrogenation of crotonaldehyde has been investigated over a monometallic Pt/SiO 2 catalyst and platinum bimetallic catalysts where the second metal was either silver, copper, or tin. The effects of addition of a second metal to the Pt/SiO 2 system on the selectivity to crotyl alcohol were investigated. The Pt-Sn bimetallic catalysts were characterized by hydrogen chemisorption, 1H NMR and microcalorimetry. The Pt-Ag/SiO 2 and Pt-Cu/SiO 2 catalysts were characterized by hydrogen chemisorption. Pt-Sn/SiO 2 catalysts selectively hydrogenated crotonaldehyde to crotyl alcohol and the method of preparation of these catalysts affected the selectivity. The most selective Pt-Sn/SiO 2 catalystsmore » for the hydrogenation of crotonaldehyde to crotyl alcohol were those in which the Sn precursor was dissolved in a HCl solution. Sn increased both the rate of formation of butyraldehyde and the rate of formation of crotyl alcohol. The Pt/SiO 2, Pt-Ag/SiO 2 and Pt-Cu/SiO 2 catalysts produced only butyraldehyde. Initial heats of adsorption (~90 kJ/mol) measured using microcalorimetry were not affected by the presence of Sn on Pt. We can conclude that there is no through metal electronic interaction between Pt and Sn at least with respect to hydrogen surface bonds since the Pt and Pt-Sn at least with respect to hydrogen surface bonds since the Pt and Pt-Sn had similar initial heats of adsorption coupled with the invariance of the 1H NMR Knight shift.« less

Bifunctional catalyst of graphite-encapsulated iron compound nanoparticle for magnetic carbon nanotubes growth by chemical vapor deposition

NASA Astrophysics Data System (ADS)

Saraswati, Teguh Endah; Prasiwi, Oktaviana Dewi Indah; Masykur, Abu; Anwar, Miftahul

2017-01-01

The carbon nanotube has widely taken great attractive in carbon nanomaterial research and application. One of its preparation methods is catalytic chemical vapor deposition (CCVD) using catalyst i.e. iron, nickel, etc. Generally, except the catalyst, carbon source gasses as the precursor are still required. Here, we report the use of the bifunctional material of Fe3O4/C which has an incorporated core/shell structures of carbon-encapsulated iron compound nanoparticles. The bifunctional catalyst was prepared by submerged arc discharge that simply performed using carbon and carbon/iron oxide electrodes in ethanol 50%. The prepared material was then used as a catalyst in thermal chemical vapor deposition at 800°C flown with ethanol vapor as the primer carbon source in a low-pressure condition. This catalyst might play a dual role as a catalyst and secondary carbon source for growing carbon nanotubes at the time. The synthesized products were characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD) analysis. The successful formation of carbon nanotubes was assigned by the shifted X-ray diffracted peak of carbon C(002), the iron oxides of Fe3O4 and γ-Fe2O3, and the other peaks which were highly considered to the other carbon allotropes with sp2 hybridization structures. The other assignment was studied by electron microscopy which successfully observed the presence of single-wall carbon nanotubes. In addition, the as-prepared carbon nanotubes have a magnetic property which was induced by the remaining of metal catalyst inside the CNT.

Fuel processing device

DOEpatents

Ahluwalia, Rajesh K [Burr Ridge, IL; Ahmed, Shabbir [Naperville, IL; Lee, Sheldon H. D. [Willowbrook, IL

2011-08-02

An improved fuel processor for fuel cells is provided whereby the startup time of the processor is less than sixty seconds and can be as low as 30 seconds, if not less. A rapid startup time is achieved by either igniting or allowing a small mixture of air and fuel to react over and warm up the catalyst of an autothermal reformer (ATR). The ATR then produces combustible gases to be subsequently oxidized on and simultaneously warm up water-gas shift zone catalysts. After normal operating temperature has been achieved, the proportion of air included with the fuel is greatly diminished.

Method for fast start of a fuel processor

DOEpatents

Ahluwalia, Rajesh K [Burr Ridge, IL; Ahmed, Shabbir [Naperville, IL; Lee, Sheldon H. D. [Willowbrook, IL

2008-01-29

An improved fuel processor for fuel cells is provided whereby the startup time of the processor is less than sixty seconds and can be as low as 30 seconds, if not less. A rapid startup time is achieved by either igniting or allowing a small mixture of air and fuel to react over and warm up the catalyst of an autothermal reformer (ATR). The ATR then produces combustible gases to be subsequently oxidized on and simultaneously warm up water-gas shift zone catalysts. After normal operating temperature has been achieved, the proportion of air included with the fuel is greatly diminished.

Cell module and fuel conditioner development

NASA Technical Reports Server (NTRS)

Hoover, D. Q., Jr.

1981-01-01

The test results of and post test analysis of Stack 559 are reported. The design features and construction status of Stacks 560, 561, 562 and 563 are described. The measurements of cell materials compressibility are rationalized and summarized and an explanation of their uses is given. Preliminary results of a manifold material/coating survey are given. The results of shift converter catalyst performance tests and reforming catalyst aging tests are reported. State points for full load and part load operation of the fuel conditioning subsystem tabulated. Work on the data base for the fuel conditioner ancillary subsystems is summarized.

Epoxidation of Geraniol: An Advanced Organic Experiment that Illustrates Asymmetric Synthesis

NASA Astrophysics Data System (ADS)

Bradley, Lynn M.; Springer, Joseph W.; Delate, Gregory M.; Goodman, Andrew

1997-11-01

The Sharpless epoxidation reaction is considered one of the most powerful advances in asymmetric organic synthesis (1). It is a classic example of the use of an asymmetric catalyst to provide an enantiomerically enriched mixture of epoxy alcohols. The procedure typically uses titanium(IV) tetraisopropoxide (Ti(OiPr)4) as a catalyst, a peroxide, and dialkyl tartrates to induce asymmetry in the epoxidation reaction of allylic alcohols. The experiment described in this paper illustrates the principle of asymmetric epoxidation and enables students to determine enantiomeric product ratios using chiral shift reagents and NMR spectroscopy.

Development of attrition resistant iron-based Fischer-Tropsch catalysts

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

NONE

2000-09-20

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 a steady loss of catalyst from the reactor. 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: (1) improve the performance and preparation procedure of the high activity, high attrition resistant, high alpha iron-based catalysts synthesized at Hampton University (2) seek improvements in the catalyst performance through variations in process conditions, pretreatment procedures and/or modifications in catalyst preparation steps and (3) investigate the performance in a slurry reactor. The effort during the reporting period has been devoted to effects of pretreating procedures, using H{sub 2}, CO and syngas (H{sub 2}/CO = 0.67) as reductants, on the performance (activity, selectivity and stability with time) of a precipitated iron catalyst (100Fe/5Cu/4.2K/10SiO{sub 2} on a mass basis ) during F-T synthesis were studied in a fixed-bed reactor.« less

Comparative Study of the ORR Activity and Stability of Pt and PtM (M = Ni, Co, Cr, Pd) Supported on Polyaniline/Carbon Nanotubes in a PEM Fuel Cell.

PubMed

Kaewsai, Duanghathai; Hunsom, Mali

2018-05-04

The oxygen reduction reaction (ORR) activity and stability of platinum (Pt) and PtM (M = Ni, Co, Cr, Pd) supported on polyaniline/carbon nanotube (PtM/PANI-CNT) were explored and compared with the commercial Pt/C catalyst (ETEK). The Pt/PANI-CNT catalyst exhibited higher ORR activity and stability than the commercial Pt/C catalyst even though it had larger crystallite/particle sizes, lower catalyst dispersion and lower electrochemical surface area (ESA), probably because of its high electrical conductivity. The addition of second metal (M) enhanced the ORR activity and stability of the Pt/PANI-CNT catalyst, because the added M induced the formation of a PtM alloy and shifted the d -band center to downfield, leading to a weak chemical interaction between oxygenated species and the catalyst surface and, therefore, affected positively the catalytic activity. Among all the tested M, the addition of Cr was optimal. Although it improved the ORR activity of the Pt/PANI-CNT catalyst slightly less than that of Pd (around 4.98%) in low temperature (60 °C)/pressure (1 atm abs), it reduced the ESA loss by around 14.8% after 1000 cycles of repetitive cyclic voltammetry (CV). In addition, it is cheaper than Pd metal. Thus, Cr was recommended as the second metal to alloy with Pt on the PANI-CNT support.

Comparative Study of the ORR Activity and Stability of Pt and PtM (M = Ni, Co, Cr, Pd) Supported on Polyaniline/Carbon Nanotubes in a PEM Fuel Cell

PubMed Central

Kaewsai, Duanghathai; Hunsom, Mali

2018-01-01

The oxygen reduction reaction (ORR) activity and stability of platinum (Pt) and PtM (M = Ni, Co, Cr, Pd) supported on polyaniline/carbon nanotube (PtM/PANI-CNT) were explored and compared with the commercial Pt/C catalyst (ETEK). The Pt/PANI-CNT catalyst exhibited higher ORR activity and stability than the commercial Pt/C catalyst even though it had larger crystallite/particle sizes, lower catalyst dispersion and lower electrochemical surface area (ESA), probably because of its high electrical conductivity. The addition of second metal (M) enhanced the ORR activity and stability of the Pt/PANI-CNT catalyst, because the added M induced the formation of a PtM alloy and shifted the d-band center to downfield, leading to a weak chemical interaction between oxygenated species and the catalyst surface and, therefore, affected positively the catalytic activity. Among all the tested M, the addition of Cr was optimal. Although it improved the ORR activity of the Pt/PANI-CNT catalyst slightly less than that of Pd (around 4.98%) in low temperature (60 °C)/pressure (1 atm abs), it reduced the ESA loss by around 14.8% after 1000 cycles of repetitive cyclic voltammetry (CV). In addition, it is cheaper than Pd metal. Thus, Cr was recommended as the second metal to alloy with Pt on the PANI-CNT support. PMID:29734719

Enhancement of Glycerol Steam Reforming Activity and Thermal Stability by Incorporating CeO2 and TiO2 in Ni- and Co-MCM-41 Catalysts

NASA Astrophysics Data System (ADS)

Dade, William N.

Hydrogen (H2) has many applications in industry with current focus shifted to production of hydrocarbon fuels and valuable oxygenates using the Fischer-Tropsch technology and direct use in proton exchange membrane fuel cell (PEMFC). Hydrogen is generally produced via steam reforming of natural gas or alcohols like methanol and ethanol. Glycerol, a by-product of biodiesel production process, is currently considered to be one of the most attractive sources of sustainable H2 due to its high H/C ratio and bio-based origin. Ni and Co based catalysts have been reported to be active in glycerol steam reforming (GSR); however, deactivation of the catalysts by carbon deposition and sintering under GSR operating conditions is a major challenge. In this study, a series of catalysts containing Ni and Co nanoparticles incorporated in CeO2 and TiO2 modified high surface area MCM-41 have been synthesized using one-pot method. The catalysts are tested for GSR (at H2O/Glycerol mole ratio of 12 and GHSV of 2200 h-1) to study the effect of support modification and reaction temperature (450 - 700 °C) on the product selectivity and long term stability. GSR results revealed that all the catalysts performed significantly well exhibiting over 85% glycerol conversion at 650 °C except Ni catalysts that showed better low temperature activities. Deactivation studies of the catalysts conducted at 650 °C indicated that the Ni-TiO2-MCM-41 and Ni-CeO 2-MCM-41 were resistant to deactivation with ˜100% glycerol conversion for 40 h. In contrast, Co-TiO2-MCM-41 perform poorly as the catalyst rapidly deactivated after 12 h to yield ˜20% glycerol conversion after 40 h. The WAXRD and TGA-DSC analyses of spent catalysts showed a significant amount of coke deposition that might explain catalysts deactivation. The flattening shape of the original BET type IV isotherm with drastic reduction of catalyst surface area can also be responsible for observed drop in catalysts activities.

TESOL as a Professional Community: A Half-Century of Pedagogy, Research, and Theory

ERIC Educational Resources Information Center

Canagarajah, Suresh

2016-01-01

This article reviews the developments in significant pedagogical and research domains in TESOL during the 50-year history of "TESOL Quarterly." It situates these developments in the shift from a modernist to postmodern orientation in disciplinary discourses. The article also considers the changes in modes of knowledge dissemination in…

Discourse in Flux

ERIC Educational Resources Information Center

Sfard, Anna

2005-01-01

More than 2 decades have passed since Geoffrey Saxe's first visit to Papua New Guinea, when he began his inquiry into the highly idiosyncratic counting system of Oksapmin's people. As evidenced by his account, a quarter of a century is a period long enough to make historical shifts visible. The point of departure for this commentary on…

Earth integrated design: office dormitory facility

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

Shapira, H. B.; Barnes, P. R.

1980-01-01

The generation process of the design of the Joint Institute for Heavy Ion Research is described. Architectural and energy considerations are discussed. The facility will contain living quarters for guest scientists who come to Oak Ridge to conduct short experiments and sleeping alcoves for local researchers on long experimental shifts as well as office space. (MHR)

Special Inspector General for Iraq Reconstruction. Quarterly Reports and Semiannual Report to the United States Congress

DTIC Science & Technology

2009-01-30

focus has been, and is, shifting from major reconstruction into helping with gover - nance, helping with capacity, helping with policy reform, and...extractive industries, including oil, gas, and minerals agriculture tourism In December, a U.S. Treasury and execution. The team met with the chief

Production of hydrogen from biomass by catalytic steam reforming of fast pyrolysis oil

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

Czernik, S.; Wang, D.; Chornet, E.

1998-08-01

Hydrogen is the prototype of the environmentally cleanest fuel of interest for power generation using fuel cells and for transportation. The thermochemical conversion of biomass to hydrogen can be carried out through two distinct strategies: (a) gasification followed by water-gas shift conversion, and (b) catalytic steam reforming of specific fractions derived from fast pyrolysis and aqueous/steam processes of biomass. This paper presents the latter route that begins with fast pyrolysis of biomass to produce bio-oil. This oil (as a whole or its selected fractions) can be converted to hydrogen via catalytic steam reforming followed by a water-gas shift conversion step.more » Such a process has been demonstrated at the bench scale using model compounds, poplar oil aqueous fraction, and the whole pyrolysis oil with commercial Ni-based steam reforming catalysts. Hydrogen yields as high as 85% have been obtained. Catalyst initial activity can be recovered through regeneration cycles by steam or CO{sub 2} gasification of carbonaceous deposits.« less

Pulse studies to decipher the role of surface morphology in CuO/CeO₂ nanocatalysts for the water gas shift reaction

DOE PAGES

Rodriguez, Jose A.; Zhao, Fuzhen; Liu, Zongyuan; ...

2015-01-23

The water-gas shift reaction (WGS, CO + H₂O → CO₂) was studied over CuO/CeO₂ catalysts with two different ceria particle morphohologies, in the form of nanospheres (ns) and nanocubes (nc). To understand the strong dependence of the WGS reaction activity on the ceria nanoshapes, pulses of CO (without and with water vapor) were employed during in situ X-ray diffraction (XRD) and X-ray absoprtion near edge structure (XANES) measurements done to characterize the catalysts. The results showed that CuO/CeO₂ (ns) exhibited a substantially better activity than CuO/CeO₂ (nc). The higher activity was associated with the unique properties of CuO/CeO₂ (ns), suchmore » as the easier reduction of highly dispersed CuO to metallic Cu, the stability of metallic Cu and a larger concentration Ce³⁺ in CeO₂ (ns).« less

Chemistry and catalysis of coal liquefaction catalytic and thermal upgrading of coal liquid and hydrogenation of CO to produce fuels. Quarterly progress report, July-September 1980

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

Wiser, W.H.

1981-02-01

Studies on the basic properties of supported sulfide catalysts showed that different supports have a profound influence on catalytic activities of CoMo catalysts. The three functions of hydrodesulfurization, hydrogenation and cracking were differently affected depending on the support used and the manner of preparation of the catalyst. Also, incorporation of additives to the support showed that the different catalytic functions can be selectively affected. A systematic study concerned with catalytic cracking of coal-derived liquids, viz., an SRC-II middle-heavy distillate and four hydrotreated SRC-II products was carried out in the range of 375 to 500/sup 0/C (LHSV, 0.2 to 3.9 h/supmore » -1/). Hydrotreatment, even to a limited extent, results in a remarkable improvement in the yield of gasoline-range products from the SRC-II distillate. This improvement is ascribed to: (a) hydrogenolysis reactions leading to lower molecular weight feedstock components and (b) limited hydrogenation of aromatic rings leading to polycyclic feed components with sufficient concentration of hydroaromatic rings needed for effective cracking. The results with model compounds and the data on hydrogen consumption during hydrotreatment of SRC-II liquids indicate that for tricyclic, tetracyclic, and pentacyclic coal-liquid components the optimal concentration of hydroaromatic rings for effective subsequent cracking is at least two rings per molecule.« less

Evaluation of Bosch-Based Systems Using Non-Traditional Catalysts at Reduced Temperatures

NASA Technical Reports Server (NTRS)

Abney, Morgan B.; Mansell, J. Matthew

2011-01-01

Oxygen and water resupply make open loop atmosphere revitalization (AR) systems unfavorable for long-term missions beyond low Earth orbit. Crucial to closing the AR loop are carbon dioxide reduction systems with low mass and volume, minimal power requirements, and minimal consumables. For this purpose, NASA is exploring using Bosch-based systems. The Bosch process is favorable over state-of-the-art Sabatier-based processes due to complete loop closure. However, traditional operation of the Bosch required high reaction temperatures, high recycle rates, and significant consumables in the form of catalyst resupply due to carbon fouling. A number of configurations have been proposed for next-generation Bosch systems. First, alternative catalysts (catalysts other than steel wool) can be used in a traditional single-stage Bosch reactor to improve reaction kinetics and increase carbon packing density. Second, the Bosch reactor may be split into separate stages wherein the first reactor stage is dedicated to carbon monoxide and water formation via the reverse water-gas shift reaction and the second reactor stage is dedicated to carbon formation. A series system will enable maximum efficiency of both steps of the Bosch reaction, resulting in optimized operation and maximum carbon formation rate. This paper details the results of testing of both single-stage and two-stage Bosch systems with alternative catalysts at reduced temperatures. These results are compared to a traditional Bosch system operated with a steel wool catalyst.

Effects of food price shocks on child malnutrition: The Mozambican experience 2008/2009.

PubMed

Arndt, Channing; Hussain, M Azhar; Salvucci, Vincenzo; Østerdal, Lars Peter

2016-09-01

A propitiously timed household survey carried out in Mozambique over the period 2008/2009 permits us to study the relationship between shifts in food prices and child nutrition status in a low income setting. We focus on weight-for-height and weight-for-age in different survey quarters characterized by very different food price inflation rates. Using propensity score matching techniques, we find that these nutrition measures, which are sensitive in the short run, improve significantly in the fourth quarter of the survey, when the inflation rate for basic food products is low, compared to the first semester or three quarters, when food price inflation was generally high. The prevalence of underweight, in particular, falls by about 40 percent. We conclude that the best available evidence points to food penury, driven by the food and fuel price crisis combined with a short agricultural production year, as substantially increasing malnutrition amongst under-five children in Mozambique. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

A Cu/Pt Near-Surface Alloy for Water-Gas Shift Catalysis.

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

Knudsen, Jan; Nilekar, Anand U.; Vang, Ronnie T.

2007-05-01

The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. The primary route to hydrogen production from fossil fuels involves the water-gas shift (WGS) reaction, and an improvement in the efficiency of WGS catalysts could therefore lead to a major leap forward in the realization of hydrogen economy. On the basis of a combination of high-resolution scanning tunneling microscopy, X-ray photoelectron spectroscopy, and density functional theory (DFT) calculations, we suggestmore » the existence of a new thermodynamically stable Cu/Pt near-surface alloy (NSA). Temperature-programmed desorption and DFT reveal that this Cu/Pt NSA binds CO significantly more weakly than does Pt alone, thereby implying a considerable reduction in the potential for CO poisoning of the Cu/Pt NSA surface as compared to that of pure Pt. In addition, DFT calculations show that this Cu/Pt NSA is able to activate H2O easily, which is the rate-determining step for the WGS on several metal surfaces, and, at the same time, to bind the products of that reaction and formate intermediates rather weakly, thus avoiding possible poisoning of the catalyst surface. The Cu/Pt NSA is thus a promising candidate for an improved WGS catalyst.« less

Novel windows for "solar commodities": a device for CO2 reduction using plasmonic catalyst activation.

PubMed

Navarrete, Alexander; Muñoz, Sergio; Sanz-Moral, Luis M; Brandner, Juergen J; Pfeifer, Peter; Martín, Ángel; Dittmeyer, Roland; Cocero, María J

2015-01-01

A novel plasmonic reactor concept is proposed and tested to work as a visible energy harvesting device while allowing reactions to transform CO2 to be carried out. Particularly the reverse water gas shift (RWGS) reaction has been tested as a means to introduce renewable energy into the economy. The development of the new reactor concept involved the synthesis of a new composite capable of plasmonic activation with light, the development of an impregnation method to create a single catalyst reactor entity, and finally the assembly of a reaction system to test the reaction. The composite developed was based on a Cu/ZnO catalyst dispersed into transparent aerogels. This allows efficient light transmission and a high surface area for the catalyst. An effective yet simple impregnation method was developed that allowed introduction of the composites into glass microchannels. The activation of the reaction was made using LEDs that covered all the sides of the reactor allowing a high power delivery. The results of the reaction show a stable process capable of low temperature transformations.

A study on production of biodiesel using a novel solid oxide catalyst derived from waste.

PubMed

Majhi, Samrat; Ray, Srimanta

2016-05-01

The issues of energy security, dwindling supply and inflating price of fossil fuel have shifted the global focus towards fuel of renewable origin. Biodiesel, having renewable origin, has exhibited great potential as substitute for fossil fuels. The most common route of biodiesel production is through transesterification of vegetable oil in presence of homogeneous acid or base or solid oxide catalyst. But, the economics of biodiesel is not competitive with respect to fossil fuel due to high cost of production. The vegetable oil waste is a potential alternative for biodiesel production, particularly when disposal of used vegetable oil has been restricted in several countries. The present study evaluates the efficacy of a low-cost solid oxide catalyst derived from eggshell (a food waste) in transesterification of vegetable oil and simulated waste vegetable oil (SWVO). The impact of thermal treatment of vegetable oil (to simulate frying operation) on transesterification using eggshell-derived solid oxide catalyst (ESSO catalyst) was also evaluated along with the effect of varying reaction parameters. The study reported that around 90 % biodiesel yield was obtained with vegetable oil at methanol/oil molar ratio of 18:1 in 3 h reaction time using 10 % ESSO catalyst. The biodiesel produced with ESSO catalyst from SWVO, thermally treated at 150 °C for 24 h, was found to conform with the biodiesel standard, but the yield was 5 % lower compared to that of the untreated oil. The utilization of waste vegetable oil along with waste eggshell as catalyst is significant for improving the overall economics of the biodiesel in the current market. The utilization of waste for societal benefit with the essence of sustainable development is the novelty of this work.

Statistical Simulation of the Performance and Degradation of a PEMFC Membrane Electrode Assembly

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

Harvey, David; Bellemare-Davis, Alexander; Karan, Kunal

2012-07-01

A 1-D MEA Performance model was developed that considered transport of liquid water, agglomerate catalyst structure, and the statistical variation of the MEA characteristic parameters. The model was validated against a low surface area carbon supported catalyst across various platinum loadings and operational conditions. The statistical variation was found to play a significant role in creating noise in the validation data and that there was a coupling effect between movement in material properties with liquid water transport. Further, in studying the low platinum loaded catalyst layers it was found that liquid water played a significant role in the increasing themore » overall transport losses. The model was then further applied to study platinum dissolution via potential cycling accelerated stress tests, in which the platinum was found to dissolve nearest the membrane effectively resulting in reaction distribution shifts within the layer.« less

Catalysts and process developments for two-stage liquefaction. Quarterly technical progress report, January 1, 1991--March 31, 1991, report No. 40

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

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

Research under way in this project centers upon developing and evaluating catalysts and process improvements for coal liquefaction in the two-stage close-coupled catalytic process. Further experimentation was undertaken in a continuous flow unit with Black Thunder coal, where the primary goal was to determine the extent of decarboxylation and changes in the structure of the unconverted coal samples. The preliminary results indicated little conversion of the feed coal to THF solubles at 600{degrees}F, although the conversion did increase with increasing temperature up to 24% at 700{degrees}F. The level of decarboxylation was also low at the above reaction temperatures. Thus, presoakingmore » in a coal-derived solvent or even tetralin does not seem to be an effective means to achieve decarboxylation. Feedstock liquefaction studies were done with Martin Lake lignite in a two-stage continuous flow unit. Conversion to THF solubles was 82-87%. The Martin Lake lignite product was very light and no resid was produced. Sulfur levels in the product were low, although nitrogen levels were relatively high, requiring further processing by hydrotreating. An air-oxidized sample of Martin Lake lignite produced high oxygen containing resid at the expense of distillate, which clearly indicates that air oxidation of lignite is detrimental. The spent catalyst from the first stage was severely deactivated and generally, the spent catalysts from both stages were in worse condition than those from a previous run with Black Thunder coal. The completed testing results of Sandia`s NiMo/hydrous titanate oxide (NiMo/HTO) preparations are reported.« less

Advanced liquefaction using coal swelling and catalyst dispersion techniques. Quarterly progress report, July--September 1993

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

Curtis, C.W.; Gutterman, C.; Chander, S.

The overall objective of this project is to develop a new approach for the direct liquefaction of coal to produce an all-distillate product slate at a sizable cost reduction over current technology. The approach integrates coal selection, pretreatment, coal swelling with catalyst impregnation, liquefaction, product recovery with characterization, alternate bottoms processing, and carrying out a technical assessment including an economic evaluation. The primary coal of this program, Black Thunder subbituminous coal, can be effectively beneficiated to about 3.5 wt % ash using aqueous sulfurous acid pretreatment. This treated coal can be further beneficiated to about 2 wt % ash usingmore » commercially available procedures. All three coals used in this study (Black Thunder, Burning Star bituminous, and Martin Lake lignite) are effectively swelled by a number of solvents. The most effective solvents are those having hetero-functionality. laboratory- and bench-scale liquefaction experimentation is underway using swelled and catalyst impregnated coal samples. Higher coal conversions were observed for the SO{sub 2}-treated subbituminous coal than the raw coal, regardless of catalyst type. Conversions of swelled coal were highest when Molyvan L, molybdenum naphthenate, and nickel octoate, respectively, were added to the liquefaction solvent. The study of bottoms processing consists of combining the ASCOT process which consists of coupling solvent deasphalting with delayed coking to maximize the production of coal-derived liquids while rejecting solids within the coke drum. The asphalt production phase has been completed; representative product has been evaluated. The solvent system for the deasphalting process has been established. Two ASCOT tests produced overall liquid yields (63.3 wt % and 61.5 wt %) that exceeded the combined liquid yields from the vacuum tower and ROSE process.« less

Partial Compensation for Altered Auditory Feedback: A Tradeoff with Somatosensory Feedback?

ERIC Educational Resources Information Center

Katseff, Shira; Houde, John; Johnson, Keith

2012-01-01

Talkers are known to compensate only partially for experimentally-induced changes to their auditory feedback. In a typical experiment, talkers might hear their F1 feedback shifted higher (so that /[epsilon]/ sounds like /[ash]/, for example), and compensate by lowering F1 in their subsequent speech by about a quarter of that distance. Here, we…

Mutual Support: Give and Take in Canada's Aging Society = Donnant-Donnant: Soutien Mutuel Dans Une Societe Canadienne Vieillissante.

ERIC Educational Resources Information Center

Theilheimer, Ish, Ed.; Eisner, Kathy, Ed.

1996-01-01

This issue of the Canadian quarterly "Transition", in French and English language versions, examines issues related to the demographic shift Canada will experience as the baby boom generation enters "old age." Major articles in this issue are: (1) "Of Mutual Benefit," which outlines some of the challenges Canada faces…

MAPPING INDUCED POLARIZATION WITH NATURAL ELECTROMAGNETIC FIELDS FOR EXPLORATION AND RESOURCES CHARACTERIZATION BY THE MINING INDUSTRY

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

Edward Nichols

2002-05-03

In this quarter we continued the processing of the Safford IP survey data. The processing identified a time shift problem between the sites that was caused by a GPS firmware error. A software procedure was developed to identify and correct the shift, and this was applied to the data. Preliminary estimates were made of the remote referenced MT parameters, and initial data quality assessment showed the data quality was good for most of the line. The multi-site robust processing code of Egbert was linked to the new data and processing initiated.

Carbocation Rearrangement in An Electrophilic Aromatic Substitution Discovery Laboratory

ERIC Educational Resources Information Center

Polito, Victoria; Hamann, Christian S.; Rhile, Ian J.

2010-01-01

In this discovery laboratory, students performed electrophilic aromatic substitution reactions between 1,4-dimethoxybenzene and either 2-methyl-2-butanol or 3-methyl-2-butanol with sulfuric acid as a catalyst. The carbocation from 3-methyl-2-butanol undergoes a hydride shift, and hence, both reactions afford…

"Variation in Student Learning" as a Threshold Concept

ERIC Educational Resources Information Center

Meyer, Jan H. F.

2012-01-01

The Threshold Concepts Framework acts as a catalyst in faculty development activities, energising and provoking discussion by faculty about their own courses in their own disciplines, and often leading to the discovery of transformational concepts that occasion epistemic and ontological shifts in their students. The present study focuses on…

The Influence of Technology on Teaching Practices at a Catholic School

ERIC Educational Resources Information Center

Swallow, Meredith J. C.

2017-01-01

Supporting 21st century skill development calls for necessary changes in teaching practices to encourage contemporary learning outcomes. Research points toward technology integration as a catalyst for supporting shifting pedagogies necessary to enhance learning. As many Catholic educators and leaders are attempting to re-shape Catholic school…

CHLORIDE POISONING OF WATER GAS SHIFT ACTIVITY ON NICKEL CATALYSTS DURING STEAM REFORMING. (R822721C633)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

Effects of catalyst concentration and ultraviolet intensity on chemical mechanical polishing of GaN

NASA Astrophysics Data System (ADS)

Wang, Jie; Wang, Tongqing; Pan, Guoshun; Lu, Xinchun

2016-08-01

Effects of catalyst concentration and ultraviolet intensity on chemical mechanical polishing (CMP) of GaN were deeply investigated in this paper. Working as an ideal homogeneous substrate material in LED industry, GaN ought to be equipped with a smooth and flat surface. Taking the strong chemical stability of GaN into account, photocatalytic oxidation technology was adopted in GaN CMP process to realize efficient removal. It was found that, because of the improved reaction rate of photocatalytic oxidation, GaN material removal rate (MRR) increases by a certain extent with catalyst concentration increasing. Cross single line analysis on the surface after polishing by Phase Shift MicroXAM-3D was carried out to prove the better removal effect with higher catalyst concentration. Ultraviolet intensity field in H2O2-SiO2-based polishing system was established and simulated, revealing the variation trend of ultraviolet intensity around the outlet of the slurry. It could be concluded that, owing to the higher planarization efficiency and lower energy damage, the UV lamp of 125 W is the most appropriate lamp in this system. Based on the analysis, defects removal model of this work was proposed to describe the effects of higher catalyst concentration and higher power of UV lamp.

Effect of the nanosized TiO2 particles in Pd/C catalysts as cathode materials in direct methanol fuel cells.

PubMed

Choi, Mahnsoo; Han, Choonsoo; Kim, In-Tae; Lee, Ji-Jung; Lee, Hong-Ki; Shim, Joongpyo

2011-07-01

Pd-TiO2/C catalysts were prepared by impregnating titanium dioxide (TiO2) on carbon-supported Pd (Pd/C) for use as the catalyst for the oxygen reduction reaction (ORR) in direct methanol fuel cells (DMFCs). Transmission electron microscope (TEM), scanning electron microscope (SEM) and X-ray diffraction (XRD) analyses were carried to confirm the distribution, morphology and structure of Pd and TiO2 on the carbon support. In fuel cell test, we confirmed that the addition of TiO2 nanoparticles make the improved catalytic activity of oxygen reduction. The electrochemical characterization of the Pd-TiO2/C catalyst for the ORR was carried out by cyclic voltammetry (CV) in the voltage window of 0.04 V to 1.2 V with scan rate of 25 mV/s. With the increase in the crystallite size of TiO2, the peak potential for OH(ads) desorption on the surface of Pd particle shifted to higher potential. This implies that TiO2 might affect the adsorption and desorption of oxygen molecules on Pd catalyst. The performance of Pd-TiO2/C as a cathode material was found to be similar to or better performance than that of Pt/C.

Effect of different promoter precursors in a model Ru-Cs/graphite system on the catalytic selectivity for Fischer-Tropsch reaction

NASA Astrophysics Data System (ADS)

Eslava, José L.; Iglesias-Juez, Ana; Fernández-García, Marcos; Guerrero-Ruiz, Antonio; Rodríguez-Ramos, Inmaculada

2018-07-01

The effect of using two different promoter precursors on the Fischer-Tropsch synthesis was studied over cesium promoted ruthenium catalysts supported on a high surface area graphite support. In this work we reveal significant modifications in the selectivity values for Fischer-Tropsch reaction depending on the Cs promoter precursor (CsCl vs CsNO3). Specifically the bimetallic catalyst (4Ru-4Cs), prepared from nitrates both for metal and promoter precursors, showed a high selectivity to CO2 during reaction. By modifying the cesium precursor, it was possible to inhibit the water gas shift reaction, decreasing significantly the selectivity to CO2. In order to understand the chemical origin of these modifications a careful characterization of the materials was performed including: X-ray absorption near edge spectroscopy, transmission electron microscopy measurements, temperature programmed reduction studies, determination of the CO uptakes on the catalysts and the evolution of the CO adsorption heats as a function of surface coverages. It was found that upon reduction and under reaction atmosphere the promoter in the ex-nitrate catalyst appears as Cs2O which is considered responsible of the CO2 production, while in the catalysts prepared with Cs chloride the promoter remains as CsCl suffering a slight partial reduction.

Effect of nanostructured carbon support on copper electrocatalytic activity toward CO 2 electroreduction to hydrocarbon fuels

DOE PAGES

Baturina, Olga; Lu, Qin; Xu, Feng; ...

2016-11-10

The effect of support on electrocatalytic activity of Cu nanoparticles (NPs) towards CO 2 electroreduction to hydrocarbon fuels (CH 4 and C 2H 4) is investigated for three types of nanostructured carbons: single wall carbon nanotubes (SWNT), graphene (GP) and onion-like carbon (OLC). Cu/SWNT, Cu/GP and Cu/OLC composite catalysts are synthesized and characterized by X-Ray diffraction analysis, transmission electron microscopy and electrochemical surface area measurements. Electrocatalytic activities of the synthesized materials, as measured in an electrochemical cell connected to a gas chromatograph, are compared to that of Cu NPs supported on Vulcan carbon. All four catalysts demonstrate higher activity towardsmore » C 2H 4 generation vs CH 4, with production of the latter mostly suppressed on Cu NPs supported on nanostructured substrates. Onset potentials for C 2H 4 vs CH 4 generation are shifted positively by 200 mV for Cu/SWNT, Cu/GP, and Cu/OLC catalysts. The Cu/OLC catalyst is found to be superior to the other two nanostructured catalysts in terms of stability, activity and selectivity towards C 2H 4 generation. Its faradaic efficiency reached 60% at -1.8 V vs Ag/AgCl. The enhanced activity and stability of Cu/OLC catalyst can be attributed to the unique catalyst design, wherein a shell of OLC surrounds the Cu NPs such that the outer layer acts as a filter that protects the Cu surface from adsorption of undesirable species, enhances its electrocatalytic performance, and improves its viability in CO 2 electroreduction reaction.« less

Effect of nanostructured carbon support on copper electrocatalytic activity toward CO 2 electroreduction to hydrocarbon fuels

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

Baturina, Olga; Lu, Qin; Xu, Feng

The effect of support on electrocatalytic activity of Cu nanoparticles (NPs) towards CO 2 electroreduction to hydrocarbon fuels (CH 4 and C 2H 4) is investigated for three types of nanostructured carbons: single wall carbon nanotubes (SWNT), graphene (GP) and onion-like carbon (OLC). Cu/SWNT, Cu/GP and Cu/OLC composite catalysts are synthesized and characterized by X-Ray diffraction analysis, transmission electron microscopy and electrochemical surface area measurements. Electrocatalytic activities of the synthesized materials, as measured in an electrochemical cell connected to a gas chromatograph, are compared to that of Cu NPs supported on Vulcan carbon. All four catalysts demonstrate higher activity towardsmore » C 2H 4 generation vs CH 4, with production of the latter mostly suppressed on Cu NPs supported on nanostructured substrates. Onset potentials for C 2H 4 vs CH 4 generation are shifted positively by 200 mV for Cu/SWNT, Cu/GP, and Cu/OLC catalysts. The Cu/OLC catalyst is found to be superior to the other two nanostructured catalysts in terms of stability, activity and selectivity towards C 2H 4 generation. Its faradaic efficiency reached 60% at -1.8 V vs Ag/AgCl. The enhanced activity and stability of Cu/OLC catalyst can be attributed to the unique catalyst design, wherein a shell of OLC surrounds the Cu NPs such that the outer layer acts as a filter that protects the Cu surface from adsorption of undesirable species, enhances its electrocatalytic performance, and improves its viability in CO 2 electroreduction reaction.« less

Carbon capture by sorption-enhanced water-gas shift reaction process using hydrotalcite-based material

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

van Selow, E.R.; Cobden, P.D.; Verbraeken, P.A.

2009-05-15

A novel route for precombustion decarbonization is the sorption-enhanced water-gas shift (SEWGS) process. In this process carbon dioxide is removed from a synthesis gas at elevated temperature by adsorption. Simultaneously, carbon monoxide is converted to carbon dioxide by the water-gas shift reaction. The periodic adsorption and desorption of carbon dioxide is induced by a pressure swing cycle, and the cyclic capacity can be amplified by purging with steam. From previous studies is it known that for SEWGS applications, hydrotalcite-based materials are particularly attractive as sorbent, and commercial high-temperature shift catalysts can be used for the conversion of carbon monoxide. Tabletsmore » of a potassium promoted hydrotalcite-based material are characterized in both breakthrough and cyclic experiments in a 2 m tall fixed-bed reactor. When exposed to a mixture of carbon dioxide, steam, and nitrogen at 400{sup o}C, the material shows a breakthrough capacity of 1.4 mmol/g. In subsequent experiments the material was mixed with tablets of promoted iron-chromium shift catalyst and exposed to a mixture of carbon dioxide, carbon monoxide, steam, hydrogen, and nitrogen. It is demonstrated that carbon monoxide conversion can be enhanced to 100% in the presence of a carbon dioxide sorbent. At breakthrough, carbon monoxide and carbon dioxide simultaneously appear at the end of the bed. During more than 300 cycles of adsorption/reaction and desorption, the capture rate, and carbon monoxide conversion are confirmed to be stable. Two different cycle types are investigated: one cycle with a CO{sub 2} rinse step and one cycle with a steam rinse step. The performance of both SEWGS cycles are discussed.« less

From 'just the facts' to 'more theory and methods, please': The evolution of the research article in Administrative Science Quarterly, 1956-2008.

PubMed

Strang, David; Siler, Kyle

2017-08-01

This paper analyzes the surface structure of research articles published in Administrative Science Quarterly between 1956 and 2008. The period is marked by a shift from essays that interweave theory, methods and results to experimental reports that separate them. There is dramatic growth in the size of theory, methods and discussion sections, accompanied by a shrinking results section. Bibliographic references and hypotheses expand in number and become concentrated in theory sections. Article structure varies primarily with historical time and also with research design (broadly, quantitative vs. qualitative) and the author's background. We link trends in article structure to the disciplinary development of organization studies and consider its distinctive trajectory relative to physical science.

Computational Chemistry-Based Identification of Ultra-Low Temperature Water-Gas-Shift Catalysts

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

Manos Mavrikakis

2008-08-31

The current work seeks to identify novel, catalytically-active, stable, poison-resistant LWGS catalysts that retain the superior activity typical of conventional Cu catalysts but can be operated at similar or lower temperatures. A database for the Binding Energies (BEs) of the LWGS relevant species, namely CO, O and OH on the most-stable, close-packed facets of a set of 17 catalytically relevant transition metals was established. This BE data and a database of previously established segregation energies was utilized to predict the stability of bimetallic NSAs that could be synthesized by combinations of the 17 parent transition metals. NSAs that were potentiallymore » stable both in vacuo and under the influence of strong-binding WGS intermediates were then selected for adsorption studies. A set of 40 NSAs were identified that satisfied all three screener criteria and the binding energies of CO, O and OH were calculated on a set of 66, 43 and 79 NSA candidates respectively. Several NSAs were found that bound intermediates weaker than the monometallic catalysts and were thus potentially poison-resistant. Finally, kinetic studies were performed and resulted in the discovery of a specific NSA-based bimetallic catalyst Cu/Pt that is potentially a promising LWGS catalyst. This stable Cu/Pt subsurface alloy is expected to provide facile H{sub 2}O activation and remain relatively resistant from the poisoning by CO, S and formate intermediates.« less

Organometallic model complexes elucidate the active gallium species in alkane dehydrogenation catalysts based on ligand effects in Ga K-edge XANES

DOE PAGES

Getsoian, Andrew "Bean"; Das, Ujjal; Camacho-Bunquin, Jeffrey; ...

2016-06-13

Gallium-modified zeolites are known catalysts for the dehydrogenation of alkanes, reactivity that finds industrial application in the aromatization of light alkanes by Ga-ZSM5. While the role of gallium cations in alkane activation is well known, the oxidation state and coordination environment of gallium under reaction conditions has been the subject of debate. Edge shifts in Ga K-edge XANES spectra acquired under reaction conditions have long been interpreted as evidence for reduction of Ga(III) to Ga(I). However, a change in oxidation state is not the only factor that can give rise to a change in the XANES spectrum. In order tomore » better understand the XANES spectra of working catalysts, we have synthesized a series of molecular model compounds and grafted surface organometallic Ga species and compared their XANES spectra to those of gallium-based catalysts acquired under reducing conditions. We demonstrate that changes in the identity and number of gallium nearest neighbors can give rise to changes in XANES spectra similar to those attributed in literature to changes in oxidation state. Specifically, spectral features previously attributed to Ga(I) may be equally well interpreted as evidence for low-coordinate Ga(III) alkyl or hydride species. Furthermore, these findings apply both to gallium-impregnated zeolite catalysts and to silica-supported single site gallium catalysts, the latter of which is found to be active and selective for dehydrogenation of propane and hydrogenation of propylene.« less

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.

Iron-oxide Aerogel and Xerogel Catalyst Formulations: Characterization by 57Fe Mössbauer and XAFS Spectroscopies

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

Huggins, F.; Bali, S; Huffman, G

2010-01-01

Iron in various iron-oxide aerogel and xerogel catalyst formulations ({ge}85% Fe{sub 2}O{sub 3}; {le}10% K, Co, Cu, or Pd) developed for possible use in Fischer-Tropsch synthesis (FTS) or the water-gas-shift (WGS) reaction has been examined by {sup 57}Fe Moessbauer spectroscopy. The seventeen samples consisted of both as-prepared and calcined aerogels and xerogels and their products after use as catalysts for FTS or the WGS reaction. Complementary XAFS spectra were obtained on the occurrence of the secondary elements in some of the same materials. A broad, slightly asymmetric, two-peak Moessbauer spectrum was obtained from the different as-prepared and calcined catalyst formulationsmore » in the majority of cases. Such spectra could only be satisfactorily fit with three quadrupole doublet components, but no systematic trends in the isomer shift and quadrupole splitting parameters and area ratios of the individual components could be discerned that reflected variations in the composition or preparation of the aerogel or xerogel materials. However, significant reductions were noted in the Moessbauer effective thickness (recoilless absorption effect per unit mass of iron) parameter, {chi}{sub eff}/g, determined at room temperature, for aerogels and xerogels compared to bulk iron oxides, reflecting the openness and lack of rigidity of the aerogel and xerogel structures. Moessbauer measurements for two aerogels over the range from 15 to 292 K confirmed the greatly diminished nature of this parameter at room temperature. Major increases in the effective thickness parameter were observed when the open structure of the aerogel or xerogel collapsed during calcination resulting in the formation of iron oxides (hematite, spinel ferrite). Similar structural changes were indicated by increases in this parameter after use of iron-oxide aerogels as catalysts for FTS or the WGS reaction, during which the iron-oxide aerogel was converted to a mixture of nonstoichiometric magnetite and the Haegg carbide, {chi}-Fe{sub 5}C{sub 2}, or nonstoichiometric magnetite, respectively.« less

Demographic Trends in Social Work over a Quarter-Century in an Increasingly Female Profession

ERIC Educational Resources Information Center

Schilling, Robert; Morrish, Jennifer Naranjo; Liu, Gan

2008-01-01

This article depicts the changing demographic portrait of social work education in the United States from 1974 through 2000 and considers the demographic shifts in the profession of social work. During this period, BSW and joint MSW-BSW programs increased from 150 to 404, MSW programs increased from 79 to 139, and social work doctoral programs…

Artificially Expanded Genetic Information Systems for New Aptamer Technologies.

PubMed

Biondi, Elisa; Benner, Steven A

2018-05-09

Directed evolution was first applied to diverse libraries of DNA and RNA molecules a quarter century ago in the hope of gaining technology that would allow the creation of receptors, ligands, and catalysts on demand. Despite isolated successes, the outputs of this technology have been somewhat disappointing, perhaps because the four building blocks of standard DNA and RNA have too little functionality to have versatile binding properties, and offer too little information density to fold unambiguously. This review covers the recent literature that seeks to create an improved platform to support laboratory Darwinism, one based on an artificially expanded genetic information system (AEGIS) that adds independently replicating nucleotide “letters” to the evolving “alphabet”.

Nurse Knowledge Exchange Plus: Human-Centered Implementation for Spread and Sustainability.

PubMed

Lin, Mike; Heisler, Scott; Fahey, Linda; McGinnis, Juli; Whiffen, Teri L

2015-07-01

Kaiser Permanente implemented a new model of nursing communication at shift change-in the bedside nursing report known as the Nurse Knowledge Exchange (NKE) in 2004-but noted variations in its spread and sustainability across medical centers five years later. The six core elements of NKEplus were as follows: team rounding in the last hour before shift changes, pre-shift patient assignments that limit the number of departing nurses at shift change, unit support for uninterrupted bedside reporting, standardization for report and safety check formats, and collaboration with patients to update in-room care boards. In January 2011 Kaiser Permanente Southern California (KPSC; Pasadena) began implementing NKEplus in 125 nursing units across 14 hospitals, with the use of human-centered design principles: creating shared understanding of the need for change, minimum specifications, and customization by frontline staff. Champion teams on each nursing unit designed and pilot tested unit-specific versions of NKEplus for four to eight weeks. Implementation occurred in waves and proceeded from medical/surgical units to specialty units. Traditional performance improvement strategies of accountability, measurement, and management were also applied. By the end of 2012, 100% of the 64 medical/surgical units and 47 (77.0%) of the 61 specialty units in KPSC medical centers implemented NKEplus-as had all but 1 of the specialty units by May 2013. The mean KPSC score on the NKEplus nursing behavior bundle improved from 65.9% in 2010 to 71.3% in the first quarter of 2014. The mean KPSC Hospital Consumer Assessment of Healthcare Providers and Systems (HCAHPS) score for nurse communication improved from 73.1% in 2010 to 76.4% in the first quarter of 2014 (p < . 001). Human-centered implementation appeared to help spread a new model of nursing handoffs and change the culture of professional nursing practice related to shift change.

Interactive Whiteboard Use: The Catalyst of Student Achievement

ERIC Educational Resources Information Center

Lamberth, Tenneille Terrell

2012-01-01

The No Child Left Behind (NCLB) Act of 2001 forced school districts to become more accountable by requiring all students to read on grade level by the year 2014. However, President Obama's educational policy shift is allowing states to develop their own accountability and improvement system. This study examined fourth and eighth grade math…

Sulfur tolerant molten carbonate fuel cell anode and process

DOEpatents

Remick, Robert J.

1990-01-01

Molten carbonate fuel cell anodes incorporating a sulfur tolerant carbon monoxide to hydrogen water-gas-shift catalyst provide in situ conversion of carbon monoxide to hydrogen for improved fuel cell operation using fuel gas mixtures of over about 10 volume percent carbon monoxide and up to about 10 ppm hydrogen sulfide.

ATTRITION RESISTANT IRON-BASED FISCHER-TROPSCH CATALYSTS

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

JAMES G. GOODWIN, JR.; JAMES J. SPIVEY; K. JOTHIMURUGESAN

1998-09-17

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. Iron-based (Fe) catalysts are preferred catalysts for F-T when using low CO/H{sub 2} ratio synthesis gases derived from modern coal gasifiers. This is because in addition to reasonable F-T activity, the F-T catalysts also possess high water gas shift (WGS) activity. 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, making 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. The objectives of this research are to develop a better understanding of the parameters affecting attrition resistance 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. Catalyst preparations will be based on the use of spray drying and will be scalable using commercially available equipment. The research will employ among other measurements, attrition testing and F-T synthesis, including long duration slurry reactor runs in order to ascertain the degree of success of the various preparations. The goal is to develop an Fe catalyst which can be used in a SBCR having only an internal filter for separation of the catalyst from the liquid product, without sacrificing F-T activity and selectivity. The effect of silica addition via coprecipitation and as a binder to a doubly promoted Fischer-Tropsch synthesis iron catalyst (100 Fe/5 Cu/4.2 K) was studied. The catalysts were prepared by coprecipitation, followed by binder addition and drying in a 1 m diameter, 2 m tall spray dryer. The binder silica content was varied from 0 to 20 wt %. A catalyst with 12 wt % binder silica was found to have the highest attrition resistance. F-T reaction studies over 100 hours in a fixed-bed reactor showed that this catalyst maintained around 95 % CO conversion with a methane selectivity of less than 7 wt % and a C{sub 5}{sup +} selectivity of greater than 73 wt %. The effect of adding precipitated silica from 0 to 20 parts by weight to this catalyst (containing 12 wt % binder silica) was also studied. Addition of precipitated silica was found to be detrimental to attrition resistance and resulted in increased methane and reduced wax formation.« less

Spectroscopic Study of Local Interactions of Platinum in Small [CexOy]Ptx' - Clusters

NASA Astrophysics Data System (ADS)

Ray, Manisha; Kafader, Jared O.; Chick Jarrold, Caroline

2016-06-01

Cerium oxide is a good ionic conductor, and the conductivity can be enhanced with oxygen vacancies and doping. This conductivity may play an important role in the enhancement of noble or coinage metal toward the water-gas shift reaction when supported by cerium oxide. The ceria-supported platinum catalyst in particular has received much attention because of higher activity at lower temperatures (LT) compared to the most common commercial LT-WGS catalyst. We have used a combination of anion photoelectron spectroscopy and density functional theory calculations to study the interesting molecular and electronic structures and properties of cluster models of ceria-supported platinum. [CexOy]Ptx' - (x,x'=1,2 ; y≤2x') clusters exhibit evidence of ionic bonding possible because of the high electron affinity of Pt and the low ionization potential of cerium oxide clusters. In addition, Pt- is a common daughter ion resulting from photodissociation of [CexOy]Ptx' - clusters. Finally, several of the anion and neutral clusters have profoundly different structures. These features may play a role in the enhancement of catalytic activity toward the water-gas shift reaction.

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

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

PdCo supported on multiwalled carbon nanotubes as an anode catalyst in a microfluidic formic acid fuel cell

NASA Astrophysics Data System (ADS)

Morales-Acosta, D.; Morales-Acosta, M. D.; Godinez, L. A.; Álvarez-Contreras, L.; Duron-Torres, S. M.; Ledesma-García, J.; Arriaga, L. G.

This work reports the synthesis of Pd-based alloys of Co and their evaluation as anode materials in a microfluidic formic acid fuel cell (μFAFC). The catalysts were prepared using the impregnation method followed by thermal treatment. The synthesized catalysts contain 22 wt.% Pd on multiwalled carbon nanotubes (Pd/MWCNT) and its alloys with two Co atomic percent in the sample with 4 at.% Co (PdCo1/MWCNT) and 10 at.% Co (PdCo2/MWCNT). The role of the alloying element was determined by XRD and XPS techniques. Both catalysts were evaluated as anode materials in a μFAFC operating with different concentrations of HCOOH (0.1 and 0.5 M), and the results were compared to those obtained with Pd/MWCNT. A better performance was obtained for the cell using PdCo1/MWCNT (1.75 mW cm -2) compared to Pd/MWCNT (0.85 mW cm -2) in the presence of 0.5 M HCOOH. By means of external electrode measurements, it was also possible to observe shifts in the formic acid oxidation potential due to a fuel concentration increment (ca. 0.05 V for both PdCo1/MWCNT and PdCo2/MWCNT catalysts and 0.23 V for Pd/MWCNT) that was attributed to deactivation of the catalyst material. The maximum current densities obtained were 8 mA cm -2 and 5.2 mA cm -2 for PdCo2/MWCNT and Pd/MWCNT, respectively. In this way, the addition of Co to the Pd catalyst was shown to improve the tolerance of intermediates produced during formic acid oxidation that tend to poison Pd, thus improving the catalytic activity and stability of the cell.

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

PubMed

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

2018-06-26

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

THE DIALOGICAL SELF IN PSYCHOANALYSIS.

PubMed

Muller, Felipe

2016-10-01

This paper describes the shift that appears to be taking place in contemporary psychoanalysis, as reflected among intersubjective approaches, from a monological conception of the self to a dialogical one. The monological self emphasizes the separation between mind, body, and external world, focusing on the representational and descriptive/referential function of language. In contrast, the dialogical self emphasizes practices, the permeable nature of relationships between subjects, and the constitutive function of language. This paper attempts to explain the growing emphasis on the dialogical self, understood from a theoretical, metatheoretical, and technical point of view, using contemporary intersubjective approaches to illustrate this shift. © 2016 The Psychoanalytic Quarterly, Inc.

Biofuels Refining Engineering

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

Lobban, Lance

The goal of this project is the development of novel catalysts and knowledge of reaction pathways and mechanisms for conversion of biomass-based compounds to fuels that are compatible with oil-based fuels and with acceptable or superior fuel properties. The research scope included both catalysts to convert lignocellulosic biomass-based molecules (from pyrolysis) and vegetable oil-based molecules (i.e., triglycerides and fatty acid methyl esters). This project comprised five technical tasks. Each task is briefly introduced below, and major technical accomplishments summarized. Technical accomplishments were described in greater detail in the quarterly progress reports, and in even more detail in the >50 publicationsmore » acknowledging this DoE project funding (list of publications and presentations included at the end of this report). The results of this research added greatly to the knowledge base necessary for upgrading of pyrolysis oil to hydrocarbon fuels and chemicals, and for conversion of vegetable oils to fungible diesel fuel. Numerous new catalysts and catalytic reaction systems were developed for upgrading particular compounds or compound families found in the biomass-based pyrolysis oils and vegetable oils. Methods to mitigate catalyst deactivation were investigated, including novel reaction/separation systems. Performance and emission characteristics of biofuels in flames and engines were measured. Importantly, the knowledge developed from this project became the basis for a subsequent collaborative proposal led by our research group, involving researchers from the University of Wisconsin, the University of Pittsburg, and the Idaho National Lab, for the DoE Carbon, Hydrogen and Separations Efficiency (CHASE) program, which was subsequently funded (one of only four projects awarded in the CHASE program). The CHASE project examined novel catalytic processes for lignocellulosic biomass conversion as well as technoeconomic analyses for process options for maximum carbon capture and hydrogen efficiency. Our research approach combined catalyst synthesis, measurements of catalyst activity and selectivity in different reactor systems and conditions, and detailed catalyst characterization to develop fundamental understanding of reaction pathways and the capability to predict product distributions. Nearly all of the candidate catalysts were prepared in-house via standard techniques such as impregnation, co-impregnation, or chemical vapor deposition. Supports were usually purchased, but in some cases coprecipitation was used to simultaneously create the support and active component, which can be advantageous for strong active component-support interactions and for achieving high active component dispersion. In-house synthesis also allowed for studies of the effects on catalyst activity and selectivity of such factors as support porosity, calcination temperature, and reduction/activation conditions. Depending on the physical characteristics of the molecule, catalyst activity measurements were carried out in tubular flow reactors (for vapor phase reactions) or stirred tank reactors (for liquid phase reactions) over a wide range of pressures and temperatures. Reactant and product concentrations were measured using gas chromatography (both on-line and off-line, with TCD, FID, and/or mass spectrometric detection). For promising catalysts, detailed physicochemical characterization was carried out using FTIR, Raman, XPS, and XRD spectroscopies (all available in our laboratories) and TEM spectroscopy (available at OU). Additional methods included temperature programmed techniques (TPD, TPO) and surface area measurements by nitrogen adsorption techniques.« less

Ziegler-Natta Catalyst Based on MgCl₂/Clay/ID/TiCl₄ for the Synthesis of Spherical Particles of Polypropylene Nanocomposites.

PubMed

Cardoso, Renata da Silva; Oliveira, Jaqueline da Silva; Ramis, Luciana Bortolin; Marques, Maria de Fátima V

2018-07-01

In the present work, we have designed MgCl2/clay/internal donor (ID)/TiCl4 based bisupported Ziegler-Natta catalysts containing varying amounts of organoclay (montmorillonite) in order to synthesize spherical particles of polypropylene/clay nanocomposites (PCN). The organoclay was introduced into the catalyst support formulation and PCN was obtained using the in situ polymerization technique. Decreasing the reaction time, it was possible to obtain nanocomposites with high concentrations of clay (masterbatches). Micrographs of SEM confirmed the spherical morphology of the catalysts. In addition, XRD patterns show that the active sites for polymerization were inserted in the clay galleries. The catalytic performance was evaluated in slurry propylene polymerization using triethylaluminium as cocatalyst and silane as external electron donor at 70 °C, 4 bar, and different reaction times. The PCNs obtained containing different clay amounts were characterized by X-ray diffraction, thermal analyses, transmission electronic microscopy, and extractables in heptane. The results revealed that the synthesized PP/clay particles were also spherical showing that the morphological control is possible even using catalysts containing high amounts of clay. The PCN presented high degradation temperature (459 °C). The XRD peak related to the clay interlamellar distance has shifted to lower angles, and TEM images confirmed the formation of exfoliated/intercalated clay on the PP matrix and absence of microparticles of clay.

Series-Bosch Technology for Oxygen Recovery During Lunar or Martian Surface Missions

NASA Technical Reports Server (NTRS)

Abney, Morgan B.; Mansell, J. Matthew; Rabenberg, Ellen; Stanley, Christine M.; Edmunson, Jennifer; Alleman, James E.; Chen, Kevin; Dumez, Sam

2014-01-01

Long-duration surface missions to the Moon or Mars will require life support systems that maximize resource recovery to minimize resupply from Earth. To address this need, NASA previously proposed a Series-Bosch (S-Bosch) oxygen recovery system, based on the Bosch process, which can theoretically recover 100% of the oxygen from metabolic carbon dioxide. Bosch processes have the added benefits of the potential to recover oxygen from atmospheric carbon dioxide and the use of regolith materials as catalysts, thereby eliminating the need for catalyst resupply from Earth. In 2012, NASA completed an initial design for an S-Bosch development test stand that incorporates two catalytic reactors in series including a Reverse Water-Gas Shift (RWGS) Reactor and a Carbon Formation Reactor (CFR). In 2013, fabrication of system components, with the exception of a CFR, and assembly of the test stand was initiated. Stand-alone testing of the RWGS reactor was completed to compare performance with design models. Continued testing of Lunar and Martian regolith simulants provided sufficient data to design a CFR intended to utilize these materials as catalysts. Finally, a study was conducted to explore the possibility of producing bricks from spent regolith catalysts. The results of initial demonstration testing of the RWGS reactor, results of continued catalyst performance testing of regolith simulants, and results of brick material properties testing are reported. Additionally, design considerations for a regolith-based CFR are discussed.

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

Getsoian, Andrew "Bean"; Das, Ujjal; Camacho-Bunquin, Jeffrey

Gallium-modified zeolites are known catalysts for the dehydrogenation of alkanes, reactivity that finds industrial application in the aromatization of light alkanes by Ga-ZSM5. While the role of gallium cations in alkane activation is well known, the oxidation state and coordination environment of gallium under reaction conditions has been the subject of debate. Edge shifts in Ga K-edge XANES spectra acquired under reaction conditions have long been interpreted as evidence for reduction of Ga(III) to Ga(I). However, a change in oxidation state is not the only factor that can give rise to a change in the XANES spectrum. In order tomore » better understand the XANES spectra of working catalysts, we have synthesized a series of molecular model compounds and grafted surface organometallic Ga species and compared their XANES spectra to those of gallium-based catalysts acquired under reducing conditions. We demonstrate that changes in the identity and number of gallium nearest neighbors can give rise to changes in XANES spectra similar to those attributed in literature to changes in oxidation state. Specifically, spectral features previously attributed to Ga(I) may be equally well interpreted as evidence for low-coordinate Ga(III) alkyl or hydride species. Furthermore, these findings apply both to gallium-impregnated zeolite catalysts and to silica-supported single site gallium catalysts, the latter of which is found to be active and selective for dehydrogenation of propane and hydrogenation of propylene.« less

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

Getsoian, Andrew “Bean”; Das, Ujjal; Camacho-Bunquin, Jeffrey

Gallium-modified zeolites are known catalysts for the dehydrogenation of alkanes, reactivity that finds industrial application in the aromatization of light alkanes by Ga-ZSM5. While the role of gallium cations in alkane activation is well known, the oxidation state and coordination environment of gallium under reaction conditions has been the subject of debate. Edge shifts in Ga K-edge XANES spectra acquired under reaction conditions have long been interpreted as evidence for reduction of Ga(III) to Ga(I). However, a change in oxidation state is not the only factor that can give rise to a change in the XANES spectrum. In order tomore » better understand the XANES spectra of working catalysts, we have synthesized a series of molecular model compounds and grafted surface organometallic Ga species and compared their XANES spectra to those of gallium-based catalysts acquired under reducing conditions. We demonstrate that changes in the identity and number of gallium nearest neighbors can give rise to changes in XANES spectra similar to those attributed in literature to changes in oxidation state. Specifically, spectral features previously attributed to Ga(I) may be equally well interpreted as evidence for low-coordinate Ga(III) alkyl or hydride species. These findings apply both to gallium-impregnated zeolite catalysts and to silica-supported single site gallium catalysts, the latter of which is found to be active and selective for dehydrogenation of propane and hydrogenation of propylene.« less

Series-Bosch Technology for Oxygen Recovery During Lunar or Martian Surface Missions

NASA Technical Reports Server (NTRS)

Abney, Morgan B.; Mansell, James M.; Stanley, Christine; Edmunson, Jennifer; Dumez, Samuel; Chen, Kevin; Alleman, James E.

2014-01-01

Long-duration surface missions to the Moon or Mars will require life support systems that maximize resource recovery to minimize resupply from Earth. To address this need, NASA previously proposed a Series-Bosch (S-Bosch) oxygen recovery system, based on the Bosch process, which can theoretically recover 100% of the oxygen from metabolic carbon dioxide. Bosch processes have the added benefits of the potential to recover oxygen from atmospheric carbon dioxide and the use of regolith materials as catalysts, thereby eliminating the need for catalyst resupply from Earth. In 2012, NASA completed an initial design for an S-Bosch development test stand that incorporates two catalytic reactors in series including a Reverse Water-Gas Shift (RWGS) Reactor and a Carbon Formation Reactor (CFR). In 2013, fabrication of system components, with the exception of a CFR, and assembly of the test stand was initiated. Stand-alone testing of the RWGS reactor was completed to compare performance with design models. Continued testing of Lunar and Martian regolith simulants provided sufficient data to design a CFR intended to utilize these materials as catalysts. Finally, a study was conducted to explore the possibility of producing bricks from spend regolith catalysts. The results of initial demonstration testing of the RWGS reactor, results of continued catalyst performance testing of regolith simulants, and results of brick material properties testing are reported. Additionally, design considerations for a regolith-based CFR are discussed.

Catalytic performance of heterogeneous Rh/C3N4 for the carbonylation of methanol

NASA Astrophysics Data System (ADS)

Budiman, Anatta Wahyu; Choi, Myoung Jae; Nur, Adrian

2018-02-01

The excess of water in homogeneous the carbonylation of methanol system could increase the amount of by-products formed through water-gas shift reaction and could accelerate the rusting of equipment. Many scientists tried to decrease the content of water in the carbonylation of methanol system by using lithium and iodide promoter that results a moderate catalytic activity in the water content at 2wt%. The heterogenized catalyst offers several distinct advantages such as it was enables increased catalyst concentration in the reaction mixture, which is directly proportional to acetic acid production rate, without the addition of an alkali iodide salt promoter. The heterogeneous catalyst also results in reduced by-product formation. This study is aimed to produce a novel catalyst (Rh/C3N4) with a high selectivity of acetic acid in a relatively lower water and halide content. This novel catalyst performs high conversion and selectivity of acetic acid as the result of the strong ionic bonding of melamine and rhodium complex species that was caused by the presence of methyl iodide species. The CO2 in feed gas significantly decreases the catalytic activity of Rh-melamine because of its inert characteristics. The kinetic test was performed as that the first order kinetic equation. The kinetic tests revealed the reaction route of the the carbonylation of methanol in this system was performed trough the methyl acetate.

Hydrodesulphurization of Light Gas Oil using hydrogen from the Water Gas Shift Reaction

NASA Astrophysics Data System (ADS)

Alghamdi, Abdulaziz

2009-12-01

The production of clean fuel faces the challenges of high production cost and complying with stricter environmental regulations. In this research, the ability of using a novel technology of upgrading heavy oil to treat Light Gas Oil (LGO) will be investigated. The target of this project is to produce cleaner transportation fuel with much lower cost of production. Recently, a novel process for upgrading of heavy oil has been developed at University of Waterloo. It is combining the two essential processes in bitumen upgrading; emulsion breaking and hydroprocessing into one process. The water in the emulsion is used to generate in situ hydrogen from the Water Gas Shift Reaction (WGSR). This hydrogen can be used for the hydrogenation and hydrotreating reaction which includes sulfur removal instead of the expensive molecular hydrogen. This process can be carried out for the upgrading of the bitumen emulsion which would improve its quality. In this study, the hydrodesulphurization (HDS) of LGO was conducted using in situ hydrogen produced via the Water Gas Shift Reaction (WGSR). The main objective of this experimental study is to evaluate the possibility of producing clean LGO over dispersed molybdenum sulphide catalyst and to evaluate the effect of different promoters and syn-gas on the activity of the dispersed Mo catalyst. Experiments were carried out in a 300 ml Autoclave batch reactor under 600 psi (initially) at 391°C for 1 to 3 hours and different amounts of water. After the hydrotreating reaction, the gas samples were collected and the conversion of carbon monoxide to hydrogen via WGSR was determined using a refinery gas analyzer. The sulphur content in liquid sample was analyzed via X-Ray Fluorescence. Experimental results showed that using more water will enhance WGSR but at the same time inhibits the HDS reaction. It was also shown that the amount of sulfur removed depends on the reaction time. The plan is to investigate the effect of synthesis gas (syngas) molar ratio by varying CO to H2 ratio. It is also planned to use different catalysts promoters and compare them with the un-promoted Mo based catalysts to achieve the optimum reaction conditions for treating LGO. The results of this study showed that Ni and Co have a promoting effect over unpromoted Mo catalysts for both HDS and WGSR. Ni was found to be the best promoter for both reactions. Fe showed no significant effect for both WGSR and HDS. V and K have a good promoting effect in WGSR but they inhibited the HDS reaction. Potassium was found to be the strongest inhibitor for the HDS reaction since no sulfur was removed during the reaction. Keywords. LGO, HDS, in situ H2, WGSR, oil upgrading, syn-gas.

ATTRITION RESISTANT IRON-BASED FISCHER-TROPSCH CATALYSTS

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

James G. Goodwin, Jr.; James J. Spivey; K. Jothimurugesan

1999-03-29

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. Iron-based (Fe) catalysts are preferred catalysts for F-T when using low CO/H2 ratio synthesis gases derived from modern coal gasifiers. This is because in addition to reasonable F-T activity, the F-T catalysts also possess high water gas shift (WGS) activity. However, a serious problem with themore » use of Fe catalysts in a SBCR is their tendency to undergo attrition. This can cause fouling/plugging of downstream filters and equipment, making 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. The objectives of this research are to develop a better understanding of the parameters affecting attrition resistance 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. Catalyst preparations will be based on the use of spray drying and will be scalable using commercially available equipment. The research will employ among other measurements, attrition testing and F-T synthesis, including long duration slurry reactor runs in order to ascertain the degree of success of the various preparations. The goal is to develop an Fe catalyst which can be used in a SBCR having only an internal filter for separation of the catalyst from the liquid product, without sacrificing F-T activity and selectivity. The effect of silica addition via coprecipitation and as a binder to a doubly promoted Fischer-Tropsch synthesis iron catalyst (100 Fe/5 Cu/4.2 K) was studied. The catalysts were prepared by coprecipitation, followed by binder addition and drying in a 1 m diameter, 2 m tall spray dryer. The binder silica content was varied from 0 to 20 wt %. A catalyst with 12 wt % binder silica was found to have the highest attrition resistance. F-T reaction studies over 100 hours in a fixed-bed reactor showed that this catalyst maintained around 95 % CO conversion with a methane selectivity of less than 7 wt % and a C5 + selectivity of greater than 73 wt %. The effect of adding precipitated silica from 0 to 20 parts by weight to this catalyst (containing 12 wt % binder silica) was also studied. Addition of precipitated silica was found to be detrimental to attrition resistance and resulted in increased methane and reduced wax formation. An HPR series of proprietary catalysts was prepared to further improve the attrition resistance. Based on the experience gained, a proprietary HPR-43 catalyst has been successfully spray dried in 500 g quantity. This catalyst showed 95 % CO conversion over 125 h and had less than 4 % methane selectivity. Its attrition resistance was one of the highest among the catalyst tested.« less

Catalyst support of mixed cerium zirconium titanium oxide, including use and method of making

DOEpatents

Willigan, Rhonda R [Manchester, CT; Vanderspurt, Thomas Henry [Glastonbury, CT; Tulyani, Sonia [Manchester, CT; Radhakrishnan, Rakesh [Vernon, CT; Opalka, Susanne Marie [Glastonbury, CT; Emerson, Sean C [Broad Brook, CT

2011-01-18

A durable catalyst support/catalyst is capable of extended water gas shift operation under conditions of high temperature, pressure, and sulfur levels. The support is a homogeneous, nanocrystalline, mixed metal oxide of at least three metals, the first being cerium, the second being Zr, and/or Hf, and the third importantly being Ti, the three metals comprising at least 80% of the metal constituents of the mixed metal oxide and the Ti being present in a range of 5% to 45% by metals-only atomic percent of the mixed metal oxide. The mixed metal oxide has an average crystallite size less than 6 nm and forms a skeletal structure with pores whose diameters are in the range of 4-9 nm and normally greater than the average crystallite size. The surface area of the skeletal structure per volume of the material of the structure is greater than about 240 m.sup.2/cm.sup.3. The method of making and use are also described.

Unsupported Pt-Ni Aerogels with Enhanced High Current Performance and Durability in Fuel Cell Cathodes.

PubMed

Henning, Sebastian; Ishikawa, Hiroshi; Kühn, Laura; Herranz, Juan; Müller, Elisabeth; Eychmüller, Alexander; Schmidt, Thomas J

2017-08-28

Highly active and durable oxygen reduction catalysts are needed to reduce the costs and enhance the service life of polymer electrolyte fuel cells (PEFCs). This can be accomplished by alloying Pt with a transition metal (for example Ni) and by eliminating the corrodible, carbon-based catalyst support. However, materials combining both approaches have seldom been implemented in PEFC cathodes. In this work, an unsupported Pt-Ni alloy nanochain ensemble (aerogel) demonstrates high current PEFC performance commensurate with that of a carbon-supported benchmark (Pt/C) following optimization of the aerogel's catalyst layer (CL) structure. The latter is accomplished using a soluble filler to shift the CL's pore size distribution towards larger pores which improves reactant and product transport. Chiefly, the optimized PEFC aerogel cathodes display a circa 2.5-fold larger surface-specific ORR activity than Pt/C and maintain 90 % of the initial activity after an accelerated stress test (vs. 40 % for Pt/C). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalytic behavior of metal catalysts in high-temperature RWGS reaction: In-situ FT-IR experiments and first-principles calculations

PubMed Central

Choi, Sungjun; Sang, Byoung-In; Hong, Jongsup; Yoon, Kyung Joong; Son, Ji-Won; Lee, Jong-Ho; Kim, Byung-Kook; Kim, Hyoungchul

2017-01-01

High-temperature chemical reactions are ubiquitous in (electro) chemical applications designed to meet the growing demands of environmental and energy protection. However, the fundamental understanding and optimization of such reactions are great challenges because they are hampered by the spontaneous, dynamic, and high-temperature conditions. Here, we investigated the roles of metal catalysts (Pd, Ni, Cu, and Ag) in the high-temperature reverse water-gas shift (RWGS) reaction using in-situ surface analyses and density functional theory (DFT) calculations. Catalysts were prepared by the deposition-precipitation method with urea hydrolysis and freeze-drying. Most metals show a maximum catalytic activity during the RWGS reaction (reaching the thermodynamic conversion limit) with formate groups as an intermediate adsorbed species, while Ag metal has limited activity with the carbonate species on its surface. According to DFT calculations, such carbonate groups result from the suppressed dissociation and adsorption of hydrogen on the Ag surface, which is in good agreement with the experimental RWGS results. PMID:28120896

Catalytic behavior of metal catalysts in high-temperature RWGS reaction: In-situ FT-IR experiments and first-principles calculations.

PubMed

Choi, Sungjun; Sang, Byoung-In; Hong, Jongsup; Yoon, Kyung Joong; Son, Ji-Won; Lee, Jong-Ho; Kim, Byung-Kook; Kim, Hyoungchul

2017-01-25

High-temperature chemical reactions are ubiquitous in (electro) chemical applications designed to meet the growing demands of environmental and energy protection. However, the fundamental understanding and optimization of such reactions are great challenges because they are hampered by the spontaneous, dynamic, and high-temperature conditions. Here, we investigated the roles of metal catalysts (Pd, Ni, Cu, and Ag) in the high-temperature reverse water-gas shift (RWGS) reaction using in-situ surface analyses and density functional theory (DFT) calculations. Catalysts were prepared by the deposition-precipitation method with urea hydrolysis and freeze-drying. Most metals show a maximum catalytic activity during the RWGS reaction (reaching the thermodynamic conversion limit) with formate groups as an intermediate adsorbed species, while Ag metal has limited activity with the carbonate species on its surface. According to DFT calculations, such carbonate groups result from the suppressed dissociation and adsorption of hydrogen on the Ag surface, which is in good agreement with the experimental RWGS results.

Hydrogen production by aqueous phase reforming of light oxygenated hydrocarbons

NASA Astrophysics Data System (ADS)

Shabaker, John William

Aqueous phase reforming (APR) of renewable oxygenated hydrocarbons (e.g., methanol, ethylene glycol, glycerol, sorbitol, glucose) is a promising new technology for the catalytic production of high-purity hydrogen for fuel cells and chemical processing. Supported Pt catalysts are effective catalysts for stable and rapid H2 production at temperatures near 500 K (H 2 turnover frequencies near 10 min-1). Inexpensive Raney Ni-based catalysts have been developed using a combination of fundamental and high-throughput studies that have similar catalytic properties as Pt-based materials. Promotion of Raney Ni with Sn by controlled surface reaction of organometallic tin compounds is necessary to control formation of thermodynamically-favorable alkane byproducts. Detailed characterization by Mossbauer spectroscopy, electron microscopy, adsorption studies, and x-ray photoelectron spectroscopy (XPS/ESCA) has shown that NiSn alloys are formed during heat treatment, and may be responsible for enhanced stability and selectivity for hydrogen production. Detailed kinetic studies led to the development of a kinetic mechanism for the APR reaction on Pt and NiSn catalysts, in which the oxygenate decomposes through C--H and O--H cleavage, followed by C--C cleavage and water gas shift of the CO intermediate. The rate limiting step on Pt surfaces is the initial dehydrogenation, while C--C cleavage appears rate limiting over NiSn catalysts. Tin promotion of Raney Ni catalysts suppresses C--O bond scission reactions that lead to alkane formation without inhibiting fast C--C and C--H cleavage steps that are necessary for high rates of reforming. A window of operating temperature, pressure, and reactor residence time has been identified for use of the inexpensive NiSn catalysts as a Pt substitute. Concentrated feed stocks and aggressive pretreatments have been found to counteract catalyst deactivation by sintering in the hydrothermal APR environment and allow stable, long-term production of H2 over Raney-NiSn materials.

Land Use Dynamics Involving Forestland: Trends in the U.S. South

Treesearch

Ralph J. Alig; Michael R. Dicks; Robert J. Moulton

1998-01-01

Since 1952, U.S. timberland has decreased by about 20 million acres, with about one-quarter of the reduction in the South. Although some of the timberland has been converted to urban and developed uses, Larger amounts of land shifted uses between forest and agriculture because of changes in product markets and policy conditions. We summarize area trends for major land...

Capitation funding of primary health organisations in New Zealand: are enrolled populations being funded according to need?

PubMed

Langton, Jennifer; Crampton, Peter

2008-04-18

To determine whether the three main funding formulas for Primary Health Organisations achieved a stated aim of the Primary Health Care Strategy to fund enrolled populations according to need. National data were obtained from the Ministry of Health for a 12-month period beginning in April 2004: these included demographic characteristics of the enrolled Primary Health Organisation population, plus rates tables for: First-Contact Services, Services to Improve Access, and Health Promotion. Funding for Access and Interim practices for four-quarters was calculated for each of these three funding streams. Analysis of the demographic characteristics of Access and Interim practices was undertaken. Maori and Pacific peoples made up a greater proportion of the Access population than the Interim, had higher rates of deprivation than the non-Maori/non-Pacific population, and demonstrated a younger age distribution. The first quarter (April 2004-June 2004) showed there was preferential funding for Access PHOs and in particular high-needs groups. In quarter two, this level of preferential funding had diminished, coinciding with the introduction of increased government funding for all Interim enrolees aged 65 and over. The greater funding for Access enrolees was notably eroded with the introduction of Access-level funding for those aged 65+ in Interim PHOs. Since these data were analysed all remaining Interim age groups have shifted to Access-level funding, benefiting non-Maori /non-Pacific in Interim PHOs. The rapid shift to Access-level funding for First Contact Services has seen a continued erosion of the redistributive effect of the original needs-based formulas. A system cannot be considered equitable if some members of society are not realising their health potential, and financing of primary care should remain redistributive until such a time as this objective is attained.

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

"Response to Loomis et al.:" Convergence and Uniformity in Teacher Production--A Catalyst to Create Individualistic Teacher Education Programs

ERIC Educational Resources Information Center

Nagel, Nancy G.

2008-01-01

In the essay, "The logic of convergence and uniformity in teacher production", Loomis et al. advocate that teachers are experiencing a shift from individualistic programs that prepare them toward uniform, common teacher preparation resulting from top-down agenda-setting and mandated regulations. In their theoretical stance, the knowledge…

Changing Relations between Universities and Research Policy and Industry: Catalyst or Deterrent to Unity of Europe?

ERIC Educational Resources Information Center

Wasser, Henry

European institutions of higher education must let changing economic conditions play a bigger role in their decisions about what research to emphasize. As costs escalate, constraints on government spending force a shift of funding priorities toward research of more strategic value to industry. There are many ways that universities and industry…

Development of methods to detect occurrence and effects of endocrine-disrupting chemicals: A fundamental shift in regulatory ecotoxicology

EPA Science Inventory

This is an editorial in ET&C describing the newer pathway-specific test methods for EDCs and their effect on ecotoxicology. Work conducted to support the development and application of these types of assays promises to be an important catalyst to advance the field of ecotoxicolo...

IT [Information Technology] as a Change Agent in Education and National Development.

ERIC Educational Resources Information Center

Pan, Daphne

The case of Singapore illustrates how well-deployed information technology (IT) can be a change agent in education and national development. IT has been a catalyst and enabler of the shift from didactic, passive instruction to interactive, learner-centered and learner-directed instruction. In technical education in particular, IT has served as a…

CO + H/sub 2/ reaction over nitrogen-modified iron catalysts. Quarterly technical progress report, October 1, 1983-December 30, 1983. [Denitriding of iron nitrides in both hydrogen and helium

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

Delgass, W.N.

1984-02-01

The synthesis of epsilon-Fe/sub 2.7/N is confirmed by Moessbauer spectroscopy. Carburization of epsilon-iron nitride for 2.5 hours in 3H/sub 2//CO at 523 K starts the formation of a bulk structure similar to that seen during ..gamma..'-iron nitride carburization. Reaction of ..gamma..'-Fe/sub 4/N in 3CO/H/sub 2/ synthesis gas at 523 K shows a better bulk stability than reaction in 3H/sub 2//CO. Kinetic analysis of the product distribution at the higher CO ratio confirms greater activity and selectivity maintainance. The kinetics of denitriding in both He and H/sub 2/ was studied with a mass spectrometer. Extremely rapid nitrogen loss was observed frommore » both ..gamma..'-Fe/sub 4/N and epsilon-Fe/sub 2.7/N catalysts in H/sub 2/ at 523 K. In both cases a initial exposure to H/sub 2/ produced a significant amount of NH/sub 3/ which we ascribe to an active surface species. Hydrogenation of the bulk continued with a slow rise to a maximum about 90 seconds after the introduction of H/sub 2/. The denitriding activity of the epsilon-Fe/sub 2.7/N catalyst was significantly higher than that of the ..gamma..'-Fe/sub 4/N catalyst. In contrast, the denitriding rate of epsilon-Fe/sub 2.7/N in He was significantly slower than that in H/sub 2/ until high temperatures (773K) were reached. An overall activation energy of 41.5 kcal/mol was obtained for this process. Comparison of the denitriding rate of virgin epsilon-Fe/sub 2.7/N in H/sub 2/ with that of the same nitride after five minutes of carburization during the hydrocarbon synthesis reaction indicates large differences in the overall rate. The carburized nitride was some 300 times less active to bulk hydrogenation than the virgin catalyst, which is indicative of significant changes in the first few layers of the nitride during the initial minutes of the synthesis reaction. 17 references, 5 figures.« less

Excore Modeling with VERAShift

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

Pandya, Tara M.; Evans, Thomas M.

It is important to be able to accurately predict the neutron flux outside the immediate reactor core for a variety of safety and material analyses. Monte Carlo radiation transport calculations are required to produce the high fidelity excore responses. Under this milestone VERA (specifically the VERAShift package) has been extended to perform excore calculations by running radiation transport calculations with Shift. This package couples VERA-CS with Shift to perform excore tallies for multiple state points concurrently, with each component capable of parallel execution on independent domains. Specifically, this package performs fluence calculations in the core barrel and vessel, or, performsmore » the requested tallies in any user-defined excore regions. VERAShift takes advantage of the general geometry package in Shift. This gives VERAShift the flexibility to explicitly model features outside the core barrel, including detailed vessel models, detectors, and power plant details. A very limited set of experimental and numerical benchmarks is available for excore simulation comparison. The Consortium for the Advanced Simulation of Light Water Reactors (CASL) has developed a set of excore benchmark problems to include as part of the VERA-CS verification and validation (V&V) problems. The excore capability in VERAShift has been tested on small representative assembly problems, multiassembly problems, and quarter-core problems. VERAView has also been extended to visualize these vessel fluence results from VERAShift. Preliminary vessel fluence results for quarter-core multistate calculations look very promising. Further development is needed to determine the details relevant to excore simulations. Validation of VERA for fluence and excore detectors still needs to be performed against experimental and numerical results.« less

Active Duty- U.S. Army Noise-Induced Hearing Injury Quarterly Surveillance: Q1 2010 Thru Q2 2012

DTIC Science & Technology

2014-06-10

threshold shift, tinnitus , and Noise-Induced Hearing Loss. RECOMMENDATIONS: Commanders and Preventive Medicine assets at multiple levels should use...Humes LE, Jollenbeck LM, Durch JS: Noise and military service: Implications for hearing loss and tinnitus . Washington, DC: National Academy Press...NONSPECIFIC ABNORMAL AUDITORY FUNCTION STUDIES TINN Tinnitus 38830 TINNITUS UNSPECIFIED TINN Tinnitus 38831 SUBJECTIVE TINNITUS TINN Tinnitus 38832 OBJECTIVE

Active Duty-U.S. Army Noise Induced Hearing Injury Quarterly Surveillance Q3 2011 thru Q4 2013

DTIC Science & Technology

2014-06-30

incident case rates for sensorineural hearing loss significant threshold shift, tinnitus , and Noise-Induced Hearing Loss. RECOMMENDATIONS: Commanders...2013 A-1 APPENDIX A REFERENCES Humes LE, Jollenbeck LM, Durch JS: Noise and military service: Implications for hearing loss and tinnitus . Washington...FUNCTION STUDIES TINN Tinnitus 38830 TINNITUS UNSPECIFIED TINN Tinnitus 38831 SUBJECTIVE TINNITUS TINN Tinnitus 38832 OBJECTIVE TINNITUS CPT Codes

Joint Force Quarterly. Number 3, Winter 1993-94

DTIC Science & Technology

1994-01-01

strategic bomb- ing campaigns and validity of the theory supporting them are contentious, largely be- cause many consider them an argument for shifting...and obser- vation, economic ties can be readily quantified. Recognizing that statistics are the best tool of propaganda since the warm smile, they...fatalities perhaps provided a tougher test than if many women had been captured or killed. Unlike the high, imper- sonal casualty statistics of the

Construction of the STAR Event Plane Detector

NASA Astrophysics Data System (ADS)

Adams, Joseph

2017-09-01

The Event Plane Detector (EPD) is an upgrade to the STAR experiment at RHIC, providing high granularity and acceptance in the forward (2.2 < |eta| < 5.1) region. This will improve the resolution of the event plane determination and allow selection on the collision centrality at rapidities well-separated from the midrapidity region measured by the STAR Time Projection Chamber (TPC). The EPD consists of two scintillator discs, one at positive and one at negative rapidity, 3.75 m from the center of the TPC. Each disc is segmented into 372 optically isolated tiles, read out by wavelength shifting fibers coupled to silicon photomultipliers. One quarter of a single disc was installed in STAR for the 2017 run for commissioning. In this talk I will discuss the construction of the EPD, the installation of the quarter wheel, and plans for full installation in 2018.

Synthesis, characterization and effect of calcination temperature on phase transformation and photocatalytic activity of Cu,S-codoped TiO 2 nanoparticles

NASA Astrophysics Data System (ADS)

Hamadanian, M.; Reisi-Vanani, A.; Majedi, A.

2010-01-01

A novel copper and sulfur codoped TiO 2 photocatalyst was synthesized by modified sol-gel method using titanium(IV) isopropoxide, CuCl 2·2H 2O and thiourea as precursors. The samples were characterized by X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS), scanning electron microscopy equipped with energy dispersive X-ray micro-analysis (SEM-EDX), transmission electron microscopy (TEM) and Fourier transform infrared (FT-IR) analysis. The XRD results showed undoped and Cu,S-codoped TiO 2 nanoparticles only include anatase phase. Effect of calcination temperature showed rutile phase appears in 650 and 700 °C for undoped and 0.1% Cu,S-codoped TiO 2, respectively. The SEM analysis revealed the doping of Cu and S does not leave any change in morphology of the catalyst surface. The increase of copper doping enhanced "red-shift" in the UV-vis absorption spectra. The TEM images confirmed the dopants suppressed the growth of TiO 2 grains. The photocatalytic activity of samples was tested for degradation of methyl orange (MO) solutions. The results showed photocatalytic activity of the catalysts with 0.05% Cu,0.05% S and 0.1% Cu,0.05% S were higher than that of other catalysts under ultraviolet (UV) and visible irradiation, respectively. Because of synergetic effect of S and Cu, the Cu,S-codoped TiO 2 catalyst has higher activity than undoped and Cu or S doped TiO 2 catalysts.

Synthesis of Metal-organic Frameworks Based on Zr4+ and Benzene 1,3,5-Tricarboxylate Linker as Heterogeneous Catalyst in the Esterification Reaction of Palmitic Acid

NASA Astrophysics Data System (ADS)

Larasati, I.; Winarni, D.; Putri, F. R.; Hanif, Q. A.; Lestari, W. W.

2017-07-01

The conversion of the biomass into biodiesels via catalytic esterification and trans-esterification became an interesting topic due to the depletion of fossil-based energy. Homogenous catalysts such as HCl, H2SO4 and NaOH commonly used as catalyst, however, the use of this kind of catalyst causes more problems, such as the difficulties on the separation from the product and the pollution effect on the environment. Heterogeneous catalysts, such as Metal-Organic Frameworks (MOFs) give an alternative promising way to substitute these limitations due to their strong catalytic site, porosity, high specific surface area, and easy-separation and reusable properties. Herein, we reported the synthesis of MOFs based on zirconium(IV) and H3BTC linker (H3BTC = benzene-1,3,5-tricarboxylic acid) by solvothermal and reflux method. Solvothermal reaction at 120 °C was found to be the optimum method, that was indicated by most crystalline product compared to the simulated pattern in XRD analysis. The formation of the framework was characterized by FTIR analysis, which showed a significant shift from 1722 cm-1 to 1620 cm-1. The synthesized Zr(IV)-BTC was thermally stable up to 322°C as shown by TG/DTA analysis. This high thermal stability was related to the high oxidation state of Zr(IV), which give a significant covalent character to the Zr-O bond.

Fabrication of solar light induced Fe-TiO{sub 2} immobilized on glass-fiber and application for phenol photocatalytic degradation

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

Lin, Shaohua, E-mail: linsh75@163.com; Zhang, Xiwang; Sun, Qinju

2013-11-15

Graphical abstract: - Highlights: • Fe-doped TiO{sub 2} immobilized on glass-fiber net were prepared by sol–gel method. • Fe inhibited the phase transition of TiO{sub 2} from anatase to rutile. • The optimal Fe doping dose was around 0.005 wt%. • The optimal calcination temperature was around 600 °C. - Abstract: Iron-doped anatase titanium dioxide catalysts coated on glass-fiber were successfully synthesized by a dip-coating sol–gel method. The prepared catalysts were characterized by scanning electron microscopy (SEM) with energy dispersive X-ray (EDX) analysis, X-ray diffraction (XRD), UV-Vis diffuse reflectance spectroscopy to understand the synthesis mechanism, and their photocatalytic activities weremore » evaluated by photodegradation of phenol under simulated solar irradiation. EDX analysis confirmed the existence of iron in the immobilized catalysts. XRD suggested that the phase transition of the catalysts from anatase to rutile were restrained, and almost pure anatase TiO{sub 2} could retain even the calcination temperature reached 800 °C. The UV-Vis diffuse reflectance spectroscopy of the catalysts showed a red shift and increased photoabsorbance in the visible range for all the doped samples. Iron loading and calcination temperature have obvious influences on photocatalytic activity. In this study, the optimal doping dose and calcination temperature were around 0.005 wt% and 600 °C, respectively.« less

Learning from the Starry Message: Using Galileo's "Sidereus Nuncius" in Introductory Astronomy Classes

ERIC Educational Resources Information Center

Wiesner, Matthew P.

2015-01-01

Every introductory astronomy class encounters Galileo during the course as the first man to systematically study the sky with a telescope. Every Astronomy 101 student meets Galileo as one of the major catalysts behind the shift from the Ptolemaic to the Copernican system and as one of the great minds behind the scientific method. But most of the…

Shifting from Ziegler-Natta to Philips-type catalyst? A simple and safe access to reduced titanium systems for ethylene polymerization.

PubMed

Popoff, Nicolas; Espinas, Jeff; Gouré, Eric; Boyron, Olivier; Le Roux, Erwan; Basset, Jean-Marie; Gauvin, Régis M; De Mallmann, Aimery; Taoufik, Mostafa

2011-12-01

Silica-supported titanium(IV) chloride is readily reduced by Mashima and co-workers' reagent (1-methyl-3,6-bis(trimethylsilyl)-1,4-cyclohexadiene) to afford materials active in ethylene polymerisation without need of aluminum alkyl cocatalyst. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Lei, Yu; Liu, Bin; Lu, Junling

The effect of residue chlorine on the synthesis of well-dispersed Pd nanoparticles on TiO2 supports using Pd atomic layer deposition (ALD) was investigated. The dispersion of Pd nanoparticles was compared over chlorine-containing and chlorine-free TiO2 supports prepared by selecting proper precursors. The detailed X-ray photoelectron spectroscopy and scanning transmission electron microscopy characterizations showed that higher dispersion of Pd nanoparticles was achieved on the chlorine-containing TiO2 surface than the chlorine-free TiO2. The preparation of TiO2 thin films and Pd nanoparticles was characterized by in situ FT-IR. The temperature required for complete deligation of palladium hexafluoroacetylacetonate decreased from 175 to 100 degreesmore » C with the presence of chlorine on the TiO2 surface. Density functional theory calculations confirm that Pdligand bond strength could be weakened as Pd binds to the Cl sites. The water-gas-shift reaction was chosen as the model reaction, and the catalytic performance of the ALD Pd catalysts was discussed. Compared to reported catalysts, the Pd nanocatalysts supported by TiO2/SiO2 mixed oxides showed promising performance in the low-temperature water-gas-shift reaction.« less

Photocatalytic degradation of rhodamine B, paracetamol and diclofenac sodium by supported titania-based catalysts from petrochemical residue: effect of doping with magnesium.

PubMed

da Silva, William Leonardo; Lansarin, Marla Azário; Dos Santos, João Henrique Z; Silveira, Fernando

2016-11-01

Three different lots of a residual Ziegler-Natta catalyst slurry (bearing Ti and Mg) obtained from an industrial petrochemical plant were employed as sources for the photocatalyst supported on silica. The effect of additional magnesium (1.0-25.0 wt% Mg/SiO 2 ) on the photocatalytic properties of the doped materials was investigated. Doping the titania-based photocatalyst with Mg results in a shift in the absorption threshold toward the visible spectrum. The optical band gap energy of the bare supported photocatalyst was in the range of 2.5 eV and shifted to 1.72 eV after 25 wt% Mg doping. The systems were evaluated for the photodegradation of one dye (rhodamine B (RhB)) and two drugs (paracetamol and diclofenac sodium) either under ultraviolet (UV) (365 nm - UVA) or visible radiation, separately. Among the evaluated systems, doping with 25 wt% Mg afforded the highest degradation values for the target molecules under UV and visible radiation (i.e. 87%, 60% and 55% of the RhB, paracetamol and diclofenac under UV, respectively, and 82%, 48.3% and 48% under visible irradiation, respectively).

Preparation and characterization of Bi-doped TiO{sub 2} and its solar photocatalytic activity for the degradation of isoproturon herbicide

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

Reddy, Police Anil Kumar; Srinivas, Basavaraju; Kala, Pruthu

Highlights: {yields} Visible active Bi-TiO{sub 2} photocatalyst preparation and thorough charaterization. {yields} Bi-TiO{sub 2} shows high activity for isoproturon degradation under solar light irradiation. {yields} The spectral response of TiO{sub 2} shifts from UV to visible light region by Bi doping. {yields} Bi{sup 3+{delta}+} species are playing a vital role in minimizing e{sup -}/h{sup +} recombination. -- Abstract: Bi-doped TiO{sub 2} catalyst was prepared by sol-gel method and was characterized by thermo gravimetric analysis (TGA), X-ray diffraction spectra (XRD), X-ray photo electronic spectroscopy (XPS), UV-Vis diffused reflectance spectra (DRS), photoluminescence spectra (PLS), transmission electron microscopy (TEM), energy dispersive analysis ofmore » X-rays (EDAX) and BET surface area. The photocatalytic activity of the catalysts were evaluated for the degradation of isoproturon herbicide under solar light irradiation. The UV-Visible DRS of Bi-doped TiO{sub 2} showed red shift in optical absorption. The presence of Bi{sup 3+{delta}+} species are playing a vital role in minimizing the electron hole recombination resulting higher activity compared to bare TiO{sub 2}.« less

Investigating the Surface Structure of γ-Al 2 O 3 Supported WO X Catalysts by High Field 27 Al MAS NMR and Electronic Structure Calculations

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

Wan, Chuan; Hu, Mary Y.; Jaegers, Nicholas R.

The metal-support interaction in γ-Al2O3 supported WOX catalysts is investigated by a combination of high field quantitative single pulse (SP) 27Al MAS NMR spectroscopy, 2D MQMAS, 1H-27Al CP/MAS, and electronic structure calculations. NMR allows the observation of at least seven different Al sites, including a pentahedral Al site, three different tetrahedral Al sites, and three octahedral Al sites. It is found that the penta-coordinated Al (AlP) site density decreases monotonically with an increased WOX loading while the octahedral Al (AlO) site density increases concurrently. This suggests that the Alp sites are the preferred surface anchoring positions for the WOX species.more » Importantly, the AlP site isotropic chemical shift observed for the unsupported γ-Al2O3 at about 38 ppm migrates into the octahedral region with a new isotropic chemical shift value appearing near 7 ppm when the Alp site is anchored by WOX species. Density functional theory (DFT) computational modeling of the NMR parameters on proposed cluster models is carried out to accurately interpret the dramatic chemical shift changes from which the detailed anchoring mechanisms are obtained. It is found that tungsten dimers and monomers are the preferred supported surface species on γ-Al2O3, wherein one monomeric and several dimeric structures are identified as the most likely surface anchoring structures.« less

Plasma-induced synthesis of Pt nanoparticles supported on TiO2 nanotubes for enhanced methanol electro-oxidation

NASA Astrophysics Data System (ADS)

Su, Nan; Hu, Xiulan; Zhang, Jianbo; Huang, Huihong; Cheng, Jiexu; Yu, Jinchen; Ge, Chao

2017-03-01

A Pt/C/TiO2 nanotube composite catalyst was successfully prepared for enhanced methanol electro-oxidation. Pt nanoparticles with a particle size of 2 nm were synthesized by plasma sputtering in water, and anatase TiO2 nanotubes with an inner diameter of approximately 100 nm were prepared by a simple two-step anodization method and annealing process. Field-emission scanning electron microscopy images indicated that the different morphologies of TiO2 synthesized on the surface of Ti foils were dependent on the different anodization parameters. The electrochemical performance of Pt/C/TiO2 catalysts for methanol oxidation showed that TiO2 nanotubes were more suitable for use as Pt nanoparticle support materials than irregular TiO2 short nanorods due to their tubular morphology and better electronic conductivity. X-ray photoelectron spectroscopy characterization showed that the binding energies of the Pt 4f of the Pt/C/TiO2 nanotubes exhibited a slightly positive shift caused by the relatively strong interaction between Pt and the TiO2 nanotubes, which could mitigate the poisoning of the Pt catalyst by COads, and further enhance the electrocatalytic performance. Thus, the as-obtained Pt/C/TiO2 nanotubes composites may become a promising catalyst for methanol electro-oxidation.

Simple synthesized Pt/GNs/TiO2 with good mass activity and stability for methanol oxidation

NASA Astrophysics Data System (ADS)

Zhang, Jianbo; Hu, Xiulan; Zhu, Faquan; Su, Nan; Huang, Huihong; Cheng, Jiexu; Yang, Hui

2017-12-01

Pt/GNs/TiO2 (GNs, graphene nanosheets) catalyst was synthesized by a simple two-step method, including a rapid solution plasma technique to obtained Pt nanoparticles with a size of 2-5 nm and followed by an ultrasonic mixing of the Pt, GNs and TiO2 nanoparticles. After coupling with TiO2 nanoparticles, the Pt/GNs/TiO2 catalyst exhibited a promoting catalytic activity towards methanol oxidation, which was superior to the Pt/GNs catalyst. The mass activity of the Pt/GNs/TiO2 catalyst was 3464 mA mgPt -1, which was 3.5 and 3.4 times higher than those of the Pt/GNs and the commercial Pt/C, respectively. And the Pt/GNs/TiO2 showed a strongly negative shift onset potential of methanol oxidation. The results of long-term cyclic voltammetry and CO-stripping tests showed an improved CO tolerance of the Pt/GNs/TiO2. Moreover, the mass activity of the Pt/GNs/TiO2 was further enhanced under light irradiation, with the mass activity of 4715 mA mgPt -1, which was 1.4 times higher than that of in dark. This work provides new opportunities for exploiting efficient visible photo-assisted electro-catalytic methanol oxidation.

Semi-active sliding mode control of vehicle suspension with magneto-rheological damper

NASA Astrophysics Data System (ADS)

Zhang, Hailong; Wang, Enrong; Zhang, Ning; Min, Fuhong; Subash, Rakheja; Su, Chunyi

2015-01-01

The vehicle semi-active suspension with magneto-rheological damper(MRD) has been a hot topic since this decade, in which the robust control synthesis considering load variation is a challenging task. In this paper, a new semi-active controller based upon the inverse model and sliding mode control (SMC) strategies is proposed for the quarter-vehicle suspension with the magneto-rheological (MR) damper, wherein an ideal skyhook suspension is employed as the control reference model and the vehicle sprung mass is considered as an uncertain parameter. According to the asymptotical stability of SMC, the dynamic errors between the plant and reference systems are used to derive the control damping force acquired by the MR quarter-vehicle suspension system. The proposed modified Bouc-wen hysteretic force-velocity ( F- v) model and its inverse model of MR damper, as well as the proposed continuous modulation (CM) filtering algorithm without phase shift are employed to convert the control damping force into the direct drive current of the MR damper. Moreover, the proposed semi-active sliding mode controller (SSMC)-based MR quarter-vehicle suspension is systematically evaluated through comparing the time and frequency domain responses of the sprung and unsprung mass displacement accelerations, suspension travel and the tire dynamic force with those of the passive quarter-vehicle suspension, under three kinds of varied amplitude harmonic, rounded pulse and real-road measured random excitations. The evaluation results illustrate that the proposed SSMC can greatly suppress the vehicle suspension vibration due to uncertainty of the load, and thus improve the ride comfort and handling safety. The study establishes a solid theoretical foundation as the universal control scheme for the adaptive semi-active control of the MR full-vehicle suspension decoupled into four MR quarter-vehicle sub-suspension systems.

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.

Nitrogen-doped graphene anchored with mixed growth patterns of CuPt alloy nanoparticles as a highly efficient and durable electrocatalyst for the oxygen reduction reaction in an alkaline medium.

PubMed

Illathvalappil, Rajith; Dhavale, Vishal M; Bhange, Siddheshwar N; Kurungot, Sreekumar

2017-07-06

A highly active and durable CuPt alloy catalyst with trigonal bipyramidal and truncated cube-type mixed morphologies, anchored on the nitrogen-doped graphene (NGr) surface (CuPt-TBTC/NGr), was prepared by a simple and fast method. The obtained CuPt alloy showed improved oxygen reduction reaction (ORR) activity, with a 30 mV positive shift in the half-wave potential value, as compared to the state-of-the-art Pt/C catalyst in a 0.1 M KOH solution. The CuPt alloy with the trigonal bipyramidal morphology possesses porous type inter-connected sides, which help to achieve improved mass transport of oxygen during the ORR. The exposure of the (111) plane of the CuPt alloy further improved the catalytic activity towards the dioxygen reduction in alkaline media. The ORR activity of the NGr-supported CuPt alloy was found to be dependent on the reaction time, and improved activity was obtained on the material derived at a reaction time of 90 min (CuPt-TBTC/NGr-90). The material synthesized at a lower or higher reaction time than 90 min resulted in a partially formed trigonal bipyramidal morphology with more truncated cubes or agglomerated trigonal bipyramidal and truncated cubes with closed type structures, respectively. Along with the high intrinsic ORR activity, CuPt-TBTC/NGr-90 displayed excellent electrochemical stability. Even after repeated 1000 potential cycling in a window ranging from 0.10 to 1.0 V (vs. RHE), the system clearly outperformed the state-of-the-art Pt/C catalyst with 15 and 60 mV positive shifts in the onset and half-wave potentials, respectively. CuPt-TBTC/NGr-90 also exhibited 2.1 times higher mass activity and 2.2 times higher specific activity, compared to Pt/C at 0.90 V (vs. RHE). Finally, a zinc-air battery fabricated with the alloy catalyst as the air electrode displayed a peak power density of 300 mW cm -2 , which is much higher than the peak power density of 253 mW cm -2 obtained for the state-of-the-art Pt/C catalyst as the air electrode.

Strategies for improving the performance and stability of Ni-based catalysts for reforming reactions.

PubMed

Li, Shuirong; Gong, Jinlong

2014-11-07

Owing to the considerable publicity that has been given to petroleum related economic, environmental, and political problems, renewed attention has been focused on the development of highly efficient and stable catalytic materials for the production of chemical/fuel from renewable resources. Supported nickel nanoclusters are widely used for catalytic reforming reactions, which are key processes for generating synthetic gas and/or hydrogen. New challenges were brought out by the extension of feedstock from hydrocarbons to oxygenates derivable from biomass, which could minimize the environmental impact of carbonaceous fuels and allow a smooth transition from fossil fuels to a sustainable energy economy. This tutorial review describes the recent efforts made toward the development of nickel-based catalysts for the production of hydrogen from oxygenated hydrocarbons via steam reforming reactions. In general, three challenges facing the design of Ni catalysts should be addressed. Nickel nanoclusters are apt to sinter under catalytic reforming conditions of high temperatures and in the presence of steam. Severe carbon deposition could also be observed on the catalyst if the surface carbon species adsorbed on metal surface are not removed in time. Additionally, the production of hydrogen rich gas with a low concentration of CO is a challenge using nickel catalysts, which are not so active in the water gas shift reaction. Accordingly, three strategies were presented to address these challenges. First, the methodologies for the preparation of highly dispersed nickel catalysts with strong metal-support interaction were discussed. A second approach-the promotion in the mobility of the surface oxygen-is favored for the yield of desired products while promoting the removal of surface carbon deposition. Finally, the process intensification via the in situ absorption of CO2 could produce a hydrogen rich gas with low CO concentration. These approaches could also guide the design of other types of heterogeneous base-metal catalysts for high temperature processes including methanation, dry reforming, and hydrocarbon combustion.

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.

The Strategic Shift to the Asia-Pacific

DTIC Science & Technology

2014-09-01

28 James M. Keagle, Richard D. Fisher, Jr ., and Brian Johnson, “Enhancing the U.S. Rebalance Toward Asia: Enhancing Allies,” Joint Force Quarterly...Liberation Army Air Force 2010 (Wright- Patterson AFB, OH: National Air and Space Intelligence Center, 2010), 1, http://www.au.af.mil/au/awc/awcgate...money.cnn.com/news/economy/world_economies_gdp/. Berteau, David J., Michael J. Green, Gregory T. Kiley, Nicholas F. Szechenyi, Ernest Z. Bower

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

Ren, Zhibo; Peng, Fei; Chen, Biaohua

Water-gas shift (WGS) reaction over a series of ceria-based mixed oxides supported Cu catalysts was investigated using a combined experimental and theoretical method. The mixed rod-shaped Ce 0.75M 0.25O 2 (M = Ti 4+, Zr 4+, Mn 4+) solid solutions, which majorly expose the (110) and (100) facets, are synthesized by hydrothermal method and used to prepare supported Cu catalysts. We found that the Cu/Ce0.75Ti 0.25O 2 (Cu-CT) exhibits the highest CO conversion in the temperature range of 150-250 °C among all supported Cu catalysts. This is mainly attributed to (i) good dispersion of Cu; (ii) largest amount of moderatemore » copper oxide; and (iii) strongest Cu-support interaction of Cu-CT. And compared to other mixed metals, periodic density functional theory calculations performed, this work further suggest that the introduction of Ti into CeO 2 not only promotes oxygen vacancy formation and CO adsorption, but also facilitates the carboxyl (COOH) formation at the interface of the Cu cluster and the support, which leads to the enhanced catalytic activity of the Cu-CT toward WGS reaction.« less

Direct conversion of CO2 into liquid fuels with high selectivity over a bifunctional catalyst.

PubMed

Gao, Peng; Li, Shenggang; Bu, Xianni; Dang, Shanshan; Liu, Ziyu; Wang, Hui; Zhong, Liangshu; Qiu, Minghuang; Yang, Chengguang; Cai, Jun; Wei, Wei; Sun, Yuhan

2017-10-01

Although considerable progress has been made in carbon dioxide (CO 2 ) hydrogenation to various C 1 chemicals, it is still a great challenge to synthesize value-added products with two or more carbons, such as gasoline, directly from CO 2 because of the extreme inertness of CO 2 and a high C-C coupling barrier. Here we present a bifunctional catalyst composed of reducible indium oxides (In 2 O 3 ) and zeolites that yields a high selectivity to gasoline-range hydrocarbons (78.6%) with a very low methane selectivity (1%). The oxygen vacancies on the In 2 O 3 surfaces activate CO 2 and hydrogen to form methanol, and C-C coupling subsequently occurs inside zeolite pores to produce gasoline-range hydrocarbons with a high octane number. The proximity of these two components plays a crucial role in suppressing the undesired reverse water gas shift reaction and giving a high selectivity for gasoline-range hydrocarbons. Moreover, the pellet catalyst exhibits a much better performance during an industry-relevant test, which suggests promising prospects for industrial applications.

Electride support boosts nitrogen dissociation over ruthenium catalyst and shifts the bottleneck in ammonia synthesis

DOE PAGES

Kitano, Masaaki; Kanbara, Shinji; Inoue, Yasunori; ...

2015-03-30

We actively sough novel approaches to efficient ammonia synthesis at an ambient pressure so as to reduce the cost of ammonia production and to allow for compact production facilities. It is accepted that the key is the development of a high-performance catalyst that significantly enhances dissociation of the nitrogen-nitrogen triple bond, which is generally considered a rate-determining step. Here we examine the kinetics of nitrogen and hydrogen isotope exchange and hydrogen adsorption/desorption reactions for a recently discovered efficient catalyst for ammonia synthesis --ruthenium-loaded 12CaO∙7AI 2O 3 electride (Ru/C12A7:more » $$\\bar{e}$$ )--and find that the rate controlling step of ammonia synthesis over Ru/C12A7:$$\\bar{e}$$ is not dissociation of the nitrogen-nitrogen triple bond but the subsequent formation of N-H n species. A mechanism of ammonia synthesis involving reversible storage and release of hydrogen atoms on the Ru/C12A7:$$\\bar{e}$$ surface is proposed on the basis of observed hydrogen adsorption/desorption kinetics.« less

Electride support boosts nitrogen dissociation over ruthenium catalyst and shifts the bottleneck in ammonia synthesis

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

Kitano, Masaaki; Kanbara, Shinji; Inoue, Yasunori

We actively sough novel approaches to efficient ammonia synthesis at an ambient pressure so as to reduce the cost of ammonia production and to allow for compact production facilities. It is accepted that the key is the development of a high-performance catalyst that significantly enhances dissociation of the nitrogen-nitrogen triple bond, which is generally considered a rate-determining step. Here we examine the kinetics of nitrogen and hydrogen isotope exchange and hydrogen adsorption/desorption reactions for a recently discovered efficient catalyst for ammonia synthesis --ruthenium-loaded 12CaO∙7AI 2O 3 electride (Ru/C12A7:more » $$\\bar{e}$$ )--and find that the rate controlling step of ammonia synthesis over Ru/C12A7:$$\\bar{e}$$ is not dissociation of the nitrogen-nitrogen triple bond but the subsequent formation of N-H n species. A mechanism of ammonia synthesis involving reversible storage and release of hydrogen atoms on the Ru/C12A7:$$\\bar{e}$$ surface is proposed on the basis of observed hydrogen adsorption/desorption kinetics.« less

Potassium-Promoted Molybdenum Carbide as a Highly Active and Selective Catalyst for CO2 Conversion to CO.

PubMed

Porosoff, Marc D; Baldwin, Jeffrey W; Peng, Xi; Mpourmpakis, Giannis; Willauer, Heather D

2017-06-09

The high concentration of CO 2 bound in seawater represents a significant opportunity to extract and use this CO 2 as a C 1 feedstock for synthetic fuels. Using an existing process, CO 2 and H 2 can be concurrently extracted from seawater and then catalytically reacted to produce synthetic fuel. Hydrogenating CO 2 directly into liquid hydrocarbons is exceptionally difficult, but by first identifying a catalyst for selective CO production through the reverse water-gas shift (RWGS) reaction, CO can then be hydrogenated to fuel through Fischer-Tropsch (FT) synthesis. Results of this study demonstrate that potassium-promoted molybdenum carbide supported on γ-Al 2 O 3 (K-Mo 2 C/γ-Al 2 O 3 ) is a low-cost, stable, and highly selective catalyst for RWGS over a wide range of conversions. These findings are supported by X-ray diffraction, scanning electron microscopy with energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and density functional theory calculations. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Confined Ultrathin Pd-Ce Nanowires with Outstanding Moisture and SO2 Tolerance in Methane Combustion.

PubMed

Peng, Honggen; Rao, Cheng; Zhang, Ning; Wang, Xiang; Liu, Wenming; Mao, Wenting; Han, Lu; Zhang, Pengfei; Dai, Sheng

2018-05-22

An efficient strategy (enhanced metal oxide interaction and core-shell confinement to inhibit the sintering of noble metal) is presented confined ultrathin Pd-CeO x nanowire (2.4 nm) catalysts for methane combustion, which enable CH 4 total oxidation at a low temperature of 350 °C, much lower than that of a commercial Pd/Al 2 O 3 catalyst (425 °C). Importantly, unexpected stability was observed even under harsh conditions (800 °C, water vapor, and SO 2 ), owing to the confinement and shielding effect of the porous silica shell together with the promotion of CeO 2 . Pd-CeO x solid solution nanowires (Pd-Ce NW) as cores and porous silica as shells (Pd-CeNW@SiO 2 ) were rationally prepared by a facile and direct self-assembly strategy for the first time. This strategy is expected to inspire more active and stable catalysts for use under severe conditions (vehicle emissions control, reforming, and water-gas shift reaction). © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Optimizing catalysis conditions to decrease aromatic hydrocarbons and increase alkanes for improving jet biofuel quality.

PubMed

Cheng, Jun; Li, Tao; Huang, Rui; Zhou, Junhu; Cen, Kefa

2014-04-01

To produce quality jet biofuel with high amount of alkanes and low amount of aromatic hydrocarbons, two zeolites of HY and HZSM-5 supporting Ni and Mo were used as catalysts to convert soybean oil into jet fuel. Zeolite HY exhibited higher jet range alkane selectivity (40.3%) and lower jet range aromatic hydrocarbon selectivity (23.8%) than zeolite HZSM-5 (13.8% and 58.9%). When reaction temperature increased from 330 to 390°C, yield of jet fuel over Ni-Mo/HY catalyst at 4 MPa hydrogen pressure increased from 0% to 49.1% due to the shift of reaction pathway from oligomerization to cracking reaction. Further increase of reaction temperature from 390 to 410°C resulted in increased yield of jet range aromatic hydrocarbons from 18.7% to 30%, which decreased jet fuel quality. A high yield of jet fuel (48.2%) was obtained at 1 MPa low hydrogen pressure over Ni (8 wt.%)-Mo (12 wt.%)/HY catalyst. Copyright © 2014 Elsevier Ltd. All rights reserved.

The PEMFC-integrated CO oxidation — a novel method of simplifying the fuel cell plant

NASA Astrophysics Data System (ADS)

Rohland, Bernd; Plzak, Vojtech

Natural gas and methanol are the most economical fuels for residential fuel cell power generators as well as for mobile PEM-fuel cells. However, they have to be reformed with steam into hydrogen, which is to be cleaned from CO by shift-reaction and by partial oxidation to a level of no more than 30 ppm CO. This level is set by the Pt/Ru-C-anode of the PEMFC. A higher partial oxidation reaction rate for CO than those of Pt/Ru-C can be achieved in an oxidic Au-catalyst system. In the Fe 2O 3-Au system, a reaction rate of 2·10 -3 mol CO/s g Au at 1000 ppm CO and 5% "air bleed" at 80°C is achieved. This high rate allows to construct a catalyst-sheet for each cell within a PEMFC-stack. Practical and theoretical current/voltage characteristics of PEMFCs with catalyst-sheet are presented at 1000 ppm CO in hydrogen with 5% "air bleed". This gives the possibility of simplifying the gas processor of the plant.

Inverse oxide/metal catalysts in fundamental studies and practical applications: A perspective of recent developments

DOE PAGES

Rodriguez, José A.; Liu, Ping; Graciani, Jesús; ...

2016-06-21

Inverse oxide/metal catalysts have shown to be excellent systems for studying the role of the oxide and oxide–metal interface in catalytic reactions. These systems can have special structural and catalytic properties due to strong oxide–metal interactions difficult to attain when depositing a metal on a regular oxide support. Oxide phases that are not seen or are metastable in a bulk oxide can become stable in an oxide/metal system opening the possibility for new chemical properties. Using these systems, it has been possible to explore fundamental properties of the metal–oxide interface (composition, structure, electronic state), which determine catalytic performance in themore » oxidation of CO, the water–gas shift and the hydrogenation of CO 2 to methanol. Recently, there has been a significant advance in the preparation of oxide/metal catalysts for technical or industrial applications. In conclusion, one goal is to identify methods able to control in a precise way the size of the deposited oxide particles and their structure on the metal substrate.« less

A localized surface plasmon resonance (LSPR) immunosensor for CRP detection using 4-chloro-1-naphtol (4-CN) precipitation

NASA Astrophysics Data System (ADS)

Ha, Su-Ji; Park, Jin-Ho; Byun, Ju-Young; Ahn, Young-Deok; Kim, Min-Gon

2017-07-01

In this study, C-reactive protein (CRP) was detected by monitoring of LSPR shift promoted by precipitation of 4-chloro-1-naphthol (4-CN). The precipitation occurred by horseradish peroxide (HRP) catalyst which is modified at CRP-detection antibody utilized in sandwich enzyme-linked immunosorbent assay (ELISA) on gold nano bipyramid (GNBP) substrate. Due to 4-CN precipitates which are located nearby the surface of GNBP, local refractive index (RI) and molecular density were greatly increased. This phenomenon eventually induced strong spectral red-shift of absorption band of GNBP. An excellent linear relationship (R2=0.9895) between the LSPR shift and CRP concentration was obtained in the range from 100 pg/mL to 100 ng/mL and limit of detection (LOD) was reached to 87 pg/mL.

Combustion engine system

NASA Technical Reports Server (NTRS)

Houseman, John (Inventor); Voecks, Gerald E. (Inventor)

1986-01-01

A flow through catalytic reactor which selectively catalytically decomposes methanol into a soot free hydrogen rich product gas utilizing engine exhaust at temperatures of 200 to 650 C to provide the heat for vaporizing and decomposing the methanol is described. The reactor is combined with either a spark ignited or compression ignited internal combustion engine or a gas turbine to provide a combustion engine system. The system may be fueled entirely by the hydrogen rich gas produced in the methanol decomposition reactor or the system may be operated on mixed fuels for transient power gain and for cold start of the engine system. The reactor includes a decomposition zone formed by a plurality of elongated cylinders which contain a body of vapor permeable, methanol decomposition catalyst preferably a shift catalyst such as copper-zinc.

Reactivity and Characterization of Solid State Hydrodesulfurization Catalysts.

NASA Astrophysics Data System (ADS)

Lindner, James Henry

1990-01-01

The identification of the phase responsible for hydrodesulfurization (HDS) activity has been the subject of extensive research. In this study, model solid state catalysts prepared from elemental starting materials were synthesized, characterized, and then used to desulfurize thiophene at temperatures ranging from 200-400 ^circC and a pressure of one atmosphere. The results of this work indicate that an increased HDS activity can be correlated with the presence of a poorly crystalline molybdenum sulfide-like phase detected by XRD, HREM, or AEM. The formation of this sulfur-deficient, non-stoichiometric phase could be accomplished by either removing sulfur directly from the catalyst synthesis mixture to yield a non-stoichiometric MoS_{ rm 2-x} moiety, or by introducing a transition metal promoter such as Fe, Co, Ni, or Cu into the system. The promoter atoms induced structural changes in the molybdenum sulfide edge planes by effectively scavenging sulfur during catalyst synthesis to form promoter sulfide species, which enhanced the formation of a non-stoichiometric, highly active molybdenum sulfide. This morphological effect was the primary function of the promoter in this system. All model catalysts displayed similar structure in the (0002) basal plane of MoS_2; however, only the catalytically active samples showed a high concentration of defects and disorder in the (1010), (1011), and (1012) edge planes. The HREM images obtained from these edge planes and their correlation with HDS activity dramatically illustrated the importance of the often-discussed edge plane structure of MoS_2 and its significance on HDS catalysis. Normalization of the HDS activities for the solid state models and a commercial catalyst with O_2 or CO chemisorption uptakes suggested that a similarity may exist between the catalytically active sites of these materials. In-situ XPS revealed that increasing promoter atom concentrations resulted in a more complete reduction of the promoter atom; but this shift to lower binding energies could not necessarily be correlated with activity. However, it was observed that the more active catalysts all exhibited the ability to dissociate H_2 and remove oxygen from their surface. This H_2 spillover or activation may also influence catalyst performance.

North American International Society for Microbial Electrochemical Technologies Meeting (Abstracts)

DTIC Science & Technology

2016-04-18

systems. Unlike the well-studied case of dissolved oxygen (D.O.) effects on the facultative metabolic shift between aerobic respiration and nitrate...The Pt catalyst can effectively catalyze oxygen reduction and ensure a healthy operation of bioelectrochemical systems but its high cost limits the... effect of COEs on other species in bioelectrochemical systems. Effects of additional electron acceptors in bio-anodic processes: oxygen and sulfate

Effect of second harmonic in pulse-width-modulation-based DAC for feedback of digital fluxgate magnetometer

NASA Astrophysics Data System (ADS)

Belyayev, Serhiy; Ivchenko, Nickolay

2018-04-01

Digital fluxgate magnetometers employ processing of the measured pickup signal to produce the value of the compensation current. Using pulse-width modulation with filtering for digital to analog conversion is a convenient approach, but it can introduce an intrinsic source of nonlinearity, which we discuss in this design note. A code shift of one least significant bit changes the second harmonic content of the pulse train, which feeds into the pick-up signal chain despite the heavy filtering. This effect produces a code-dependent nonlinearity. This nonlinearity can be overcome by the specific design of the timing of the pulse train signal. The second harmonic is suppressed if the first and third quarters of the excitation period pulse train are repeated in the second and fourth quarters. We demonstrate this principle on a digital magnetometer, achieving a magnetometer noise level corresponding to that of the sensor itself.

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.

Evaluation of Mn and Sn-Modified Pd-Ce-Based Catalysts for Low-Temperature Diesel Exhaust Oxidation

DOE PAGES

Wang, Chao; Binder, Andrew J.; Toops, Todd J.; ...

2016-12-07

Pd-impregnated Ce-based catalysts were tested for carbon monoxide (CO) and hydrocarbon (HC) oxidation under challenging low-temperature diesel combustion conditions. The results indicate that the light-off temperatures for CO over Pd/CeO 2, Pd/MnO x-CeO 2 (Pd/MC), and Pd/SnO 2-MnO x-CeO 2 (Pd/SMC) catalysts shift to higher temperatures in the presence of simulated diesel exhaust gas. The lowest T 50 for CO is observed over Pd/MC at 173 °C, whereas Pd/CeO 2 is shown to oxidize most of the HCs at temperatures below 400 °C. In all catalysts, the oxidation of HCs starts right after the onset of CO oxidation, revealing thatmore » the competitive adsorption of CO, NO, and alkenes controls the catalytic activity. Further evaluation of the catalytic activity in the presence of only CO and C 3H 6 reveals the immediate inhibiting effect of C 3H 6 at catalyst temperatures below 150 °C. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments performed over Pd/CeO 2, Pd/MC, and Pd/SMC show that C 3H 6 inhibits the formation of carbonyl species on Pd n+ sites, which limits the catalytic activity for CO. Lastly, such inhibition is observed on all supports, implying that the activity is independent of oxygen storage capacity (OSC) or lattice oxygen reducibility of the supports in the presence of C 3H 6.« less

Catalytic ozonation of paracetamol using commercial and Pt-supported nanocomposites of Al2O3: The impact of ultrasound.

PubMed

Ziylan-Yavaş, Asu; Ince, Nilsun H

2018-01-01

The study is the assessment of commercial γ-Al 2 O 3 and its sonolytically modified nanocomposite in catalytic ozonation of paracetamol (PCT), which is an emerging water contaminant and a highly reactive compound with ozone. The results showed that commercial alumina was ineffective regardless of the solution pH, due to the low affinity of the catalyst surface for PCT and the high reactivity of the solute with molecular ozone. The modified catalyst, which was synthesized by decoration of the original surface with nanoparticles of platinum provided considerable improvement in the performance of the catalyst, particularly in mineralization of the target compound. The presence of OH scavenging agents in solution markedly retarded the rate of PCT oxidation and organic carbon decay, to signal the importance of radical-mediated reaction mechanisms on the degradation of the compound. Finally, the attempt to accelerate the reactions by running them in the presence of ultrasound was found inadequate for the early oxidation, but highly adequate for the longer mineralization process. The failure was attributed to the diffusion of a large fraction of ozone into the gaseous cavity bubbles (reduced probability of direct reactions) and the extreme conditions of cavitation collapse that partially damaged the catalyst surface. The success (in mineralization) was explained by the shift of the reaction site from the bulk solution (poor adsorption on catalyst surfaces) to the solid surface and the gaseous cavity bubbles (via enhanced hydrophobicity), both being considerably more active reaction media. Copyright © 2017 Elsevier B.V. All rights reserved.

Evaluation of Mn and Sn-Modified Pd-Ce-Based Catalysts for Low-Temperature Diesel Exhaust Oxidation

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

Wang, Chao; Binder, Andrew J.; Toops, Todd J.

Pd-impregnated Ce-based catalysts were tested for carbon monoxide (CO) and hydrocarbon (HC) oxidation under challenging low-temperature diesel combustion conditions. The results indicate that the light-off temperatures for CO over Pd/CeO 2, Pd/MnO x-CeO 2 (Pd/MC), and Pd/SnO 2-MnO x-CeO 2 (Pd/SMC) catalysts shift to higher temperatures in the presence of simulated diesel exhaust gas. The lowest T 50 for CO is observed over Pd/MC at 173 °C, whereas Pd/CeO 2 is shown to oxidize most of the HCs at temperatures below 400 °C. In all catalysts, the oxidation of HCs starts right after the onset of CO oxidation, revealing thatmore » the competitive adsorption of CO, NO, and alkenes controls the catalytic activity. Further evaluation of the catalytic activity in the presence of only CO and C 3H 6 reveals the immediate inhibiting effect of C 3H 6 at catalyst temperatures below 150 °C. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments performed over Pd/CeO 2, Pd/MC, and Pd/SMC show that C 3H 6 inhibits the formation of carbonyl species on Pd n+ sites, which limits the catalytic activity for CO. Lastly, such inhibition is observed on all supports, implying that the activity is independent of oxygen storage capacity (OSC) or lattice oxygen reducibility of the supports in the presence of C 3H 6.« less

Biomass Conversion Strategies and the Renewable Production of Hydrogen using Heterogeneous Metal Catalysts

NASA Astrophysics Data System (ADS)

Carrasquillo-Flores, Ronald

Biomass is a renewable carbon source that can be processed into fuels and chemicals in a biorefinery. However, there are a number of challenges that need to be overcome for biomass utilization to be viable. The work presented herein aims to address two existing challenges in biomass processing schemes, namely the efficient utilization of all fractions of lignocellulosic biomass and the renewable production of the hydrogen necessary to reduce the oxygen functionalities native in biomass. First, lignin was depolymerized to produce a renewable phenolic solvent mixture. Biphasic reactions with this solvent and aqueous solution of glucose or xylose produce 5-hydroxymethylfurfural (HMF) and furfural, respectively, at high yields. HMF and furfuryl alcohol could also be upgraded into levulinic acid at high yields. The yields are due to the capacity of the solvent to partition these molecules and prevent their degradation. Second, propyl guaiacol, a component of the phenolic solvent, was used for biphasic reactions where ball milled biomass substrates were used. These substrates are converted to furfural and HMF at high yields due to the partition of these molecules into the solvent and the on-demand production of glucose and xylose from the substrate, minimizing the formation of humins. A study of the water-gas shift reaction over Pt-based catalysts was conducted. Alloying Pt with Re was found to increase the catalytic activity and microkinetic modeling revealed Pt is a good representation of the active site and Re acts as a promoter slightly destabilizing CO binding. A study on formic acid decomposition over Au catalysts was performed. Experiments, density functional theory and microkinetic modeling results indicate the reaction proceeds completely on highly undercoordinated Au atoms with any high coordination atom being largely inert. Motivated by the results on Au catalysts, the metal-support interaction was investigated for the reverse water-gas shift reaction. Using a combination of infrared spectroscopy, Raman spectroscopy, x-ray absorption spectroscopy, electron microscopy and reaction kinetics measurements it was found that the deposition of an organometallic molybdenum compound occurs at the undercoordinated Au sites to produce interfacial sites that are an order of magnitude more active than Au sites and activate water.

Hydrothermal preparation of copper doped NaTaO3 nanoparticles and study on the photocatalytic mechanism.

PubMed

Liu, Yulu; Su, Yiguo; Han, Hui; Wang, Xiaojing

2013-02-01

Effects of copper cations doping into wide band gap semiconductor photocatalysts of tantalate on morphology, visible light response, and photocatalytic performance were studied. A series of Cu-doped NaTaO3 catalysts were prepared by hydrothermal method. XRD and XPS results suggested that copper were successfully doped into the NaTaO3 nanocrystal in the Cu2+ state. TEM studies showed the formation of the cube shape nanoparticles of NaTaO3 as well as Cu-doped NaTaO3. UV-Vis diffuse reflectance spectra clearly indicated the red-shift in the series of copper doped NaTaO3 catalysts, resulting in a decrease in the band gap of NaTaO3. The trend of red shift was increased with an increase of copper doping concentration, whereas the photo-degradation methylene blue (MB) is not improved by the doping of copper ions. The simulation of energy band structure by density functional theory unfolded that the substitution of Ta5+ ions by Cu2+ ions results in forming an intermediate band (IB) upper the top of the valence band (VB), which is mainly attributed to the state of Cu 3d. The intermediate band is responsible for the red-shift caused by the doping of Cu ions. Meanwhile Cu species can become the recombination centers of photoinduced electrons and holes. Thus, the quickly recombination of e(-)h(+) pairs is one of the most significant factors which deteriorate the photoactivity of Cu-doped NaTaO3.

In-situ Characterization of Cu/CeO 2 Nanocatalysts during CO 2 Hydrogenation: Morphological Effects of Nanostructured Ceria on the Catalytic Activity

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

Lin, Lili; Yao, Siyu; Liu, Zongyuan

Here, a combination of time-resolved X-ray diffraction (TR-XRD), ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) was used to carry out an in-situ characterization of Cu/CeO 2 nanocatalysts during the hydrogenation of CO 2. Morphological effects of the ceria supports on the catalytic performances were investigated by examining the behavior of copper/ceria-nanorods (NR) and nanospheres (NS). At atmospheric pressures, the hydrogenation of CO 2 on the copper-ceria catalysts produced mainly CO through the reverse-water gas shift reaction (RWGS) and a negligible amount of methanol. The Cu/CeO 2-NR catalyst displayed the higher activity, which demonstrates thatmore » the RWGS is a structure sensitive reaction. In-situ TR-XRD and AP-XPS characterization showed significant changes in the chemical state of the catalysts under reaction conditions with the copper being fully reduced and a partial Ce 4+ to Ce 3+ transformation occurring. A more effective CO 2 dissociative activation at high temperature and a preferential formation of active bidentate carbonate and formate intermediates over CeO 2(110) terminations are probably the main reasons for the better performance of the Cu/CeO 2-NR catalyst in the RWGS reaction.« less

Homogeneously Catalyzed Electroreduction of Carbon Dioxide-Methods, Mechanisms, and Catalysts.

PubMed

Francke, Robert; Schille, Benjamin; Roemelt, Michael

2018-05-09

The utilization of CO 2 via electrochemical reduction constitutes a promising approach toward production of value-added chemicals or fuels using intermittent renewable energy sources. For this purpose, molecular electrocatalysts are frequently studied and the recent progress both in tuning of the catalytic properties and in mechanistic understanding is truly remarkable. While in earlier years research efforts were focused on complexes with rare metal centers such as Re, Ru, and Pd, the focus has recently shifted toward earth-abundant transition metals such as Mn, Fe, Co, and Ni. By application of appropriate ligands, these metals have been rendered more than competitive for CO 2 reduction compared to the heavier homologues. In addition, the important roles of the second and outer coordination spheres in the catalytic processes have become apparent, and metal-ligand cooperativity has recently become a well-established tool for further tuning of the catalytic behavior. Surprising advances have also been made with very simple organocatalysts, although the mechanisms behind their reactivity are not yet entirely understood. Herein, the developments of the last three decades in electrocatalytic CO 2 reduction with homogeneous catalysts are reviewed. A discussion of the underlying mechanistic principles is included along with a treatment of the experimental and computational techniques for mechanistic studies and catalyst benchmarking. Important catalyst families are discussed in detail with regard to mechanistic aspects, and recent advances in the field are highlighted.

Correlation between theoretical descriptor and catalytic oxygen reduction activity of graphene supported palladium and palladium alloy electrocatalysts

NASA Astrophysics Data System (ADS)

Seo, Min Ho; Choi, Sung Mook; Lee, Dong Un; Kim, Won Bae; Chen, Zhongwei

2015-12-01

The oxygen reduction reaction, ORR, performances of graphene-supported palladium (Pd) and palladium alloys (Pd3X: X = Ag, Co and Fe) catalysts with highly dispersed catalyst particles are investigated in acidic and alkaline conditions using a rotating disk electrode, RDE. Graphene nanosheet, GNS, supported Pd based catalysts are fabricated without surfactant through the impregnation of Pd and 2nd metal precursors on GNS, leading to small and uniformly dispersed nanoparticles, even when high metal loading of up to 60 wt.% are deposited on supports. The ab-initio density functional theory, DFT, calculations, which are based on the d-band center theory, have been applied to correlate with the results of the ORR performances obtained by half-cell tests. Additionally, the cohesive energy, Ecoh, and dissolution potential, Um, for the Pd nanoparticles have been calculated to understand thermodynamic stability. To elucidate the d-band center shift, the Pd 3d5/2 core-level binding energies for Pd/GNS, Pd3Ag/GNS, Pd3Fe/GNS and Pd3Co/GNS have been investigated by X-ray photoelectron spectroscopy, XPS. The GNS-supported Pd, or Pd-based alloy-nanoparticle catalyst shows good ORR activity under acidic and alkaline conditions, suggesting it may offer potential replacement for Pt for use in cathode electrodes of anion-exchange membrane fuel cell, AEMFC, and acid based polymer electrolyte fuel cell, PEMFC.

Characterization of Catalyst Materials for Production of Aerospace Fuels

NASA Technical Reports Server (NTRS)

Best, Lauren M.; De La Ree, Ana B.; Hepp, Aloysius F.

2012-01-01

Due to environmental, economic, and security issues, there is a greater need for cleaner alternative fuels. There will undoubtedly be a shift from crude oil to non-petroleum sources as a feedstock for aviation (and other transportation) fuels. Additionally, efforts are concentrated on reducing costs coupled with fuel production from non-conventional sources. One solution to this issue is Fischer-Tropsch gas-to-liquid technology. Fischer-Tropsch processing of synthesis gas (CO/H2) produces a complex product stream of paraffins, olefins, and oxygenated compounds such as alcohols and aldehydes. The Fisher-Tropsch process can produce a cleaner diesel oil fraction with a high cetane number (typically above 70) without any sulfur or aromatic compounds. This process is most commonly catalyzed by heterogeneous (in this case, silver and platinum) catalysts composed of cobalt supported on alumina or unsupported alloyed iron powders. Physisorption, chemisorptions, scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS) are described to better understand the potential performance of Fischer-Tropsch cobalt on alumina catalysts promoted with silver and platinum. The overall goal is to preferentially produce C8 to C18 paraffin compounds for use as aerospace fuels. Progress towards this goal will eventually be updated and achieved by a more thorough understanding of the characterization of catalyst materials. This work was supported by NASA s Subsonic Fixed Wing and In-situ Resource Utilization projects.

Removal of disinfection by-products from contaminated water using a synthetic goethite catalyst via catalytic ozonation and a biofiltration system.

PubMed

Wang, Yu-Hsiang; Chen, Kuan-Chung

2014-09-10

The effects of synthetic goethite (α-FeOOH) used as the catalyst in catalytic ozonation for the degradation of disinfection by-product (DBP) precursors are investigated. A biofiltration column applied following the catalytic ozonation process is used to evaluate the efficiency of removing DBP precursors via biotreatment. Ozone can rapidly react with aromatic compounds and oxidize organic compounds, resulting in a decrease in the fluorescence intensity of dissolved organic matter (DOM). In addition, catalytic ozonation can break down large organic molecules, which causes a blue shift in the emission-excitation matrix spectra. Water treated with catalytic ozonation is composed of low-molecular structures, including soluble microbial products (SMPs) and other aromatic proteins (APs). The DOM in SMPs and APs is removed by subsequent biofiltration. Catalytic ozonation has a higher removal efficiency for dissolved organic carbon and higher ultraviolet absorbance at 254 nm compared to those of ozonation without a catalyst. The use of catalytic ozonation and subsequent biofiltration leads to a lower DBP formation potential during chlorination compared to that obtained using ozonation and catalytic ozonation alone. Regarding DBP species during chlorination, the bromine incorporation factor (BIF) of trihalomethanes and haloacetic acids increases with increasing catalyst dosage in catalytic ozonation. Moreover, the highest BIF is obtained for catalytic ozonation and subsequent biofiltration.

Removal of Disinfection By-Products from Contaminated Water Using a Synthetic Goethite Catalyst via Catalytic Ozonation and a Biofiltration System·

PubMed Central

Wang, Yu-Hsiang; Chen, Kuan-Chung

2014-01-01

The effects of synthetic goethite (α-FeOOH) used as the catalyst in catalytic ozonation for the degradation of disinfection by-product (DBP) precursors are investigated. A biofiltration column applied following the catalytic ozonation process is used to evaluate the efficiency of removing DBP precursors via biotreatment. Ozone can rapidly react with aromatic compounds and oxidize organic compounds, resulting in a decrease in the fluorescence intensity of dissolved organic matter (DOM). In addition, catalytic ozonation can break down large organic molecules, which causes a blue shift in the emission-excitation matrix spectra. Water treated with catalytic ozonation is composed of low-molecular structures, including soluble microbial products (SMPs) and other aromatic proteins (APs). The DOM in SMPs and APs is removed by subsequent biofiltration. Catalytic ozonation has a higher removal efficiency for dissolved organic carbon and higher ultraviolet absorbance at 254 nm compared to those of ozonation without a catalyst. The use of catalytic ozonation and subsequent biofiltration leads to a lower DBP formation potential during chlorination compared to that obtained using ozonation and catalytic ozonation alone. Regarding DBP species during chlorination, the bromine incorporation factor (BIF) of trihalomethanes and haloacetic acids increases with increasing catalyst dosage in catalytic ozonation. Moreover, the highest BIF is obtained for catalytic ozonation and subsequent biofiltration. PMID:25211774

Developing physicians as catalysts for change.

PubMed

George, Aaron E; Frush, Karen; Michener, J Lloyd

2013-11-01

Failures in care coordination are a reflection of larger systemic shortcomings in communication and in physician engagement in shared team leadership. Traditional medical care and medical education neither focus on nor inspire responses to the challenges of coordinating care across episodes and sites. The authors suggest that the absence of attention to gaps in the continuum of care has led physicians to attempt to function as the glue that holds the health care system together. Further, medical students and residents have little opportunity to provide feedback on care processes and rarely receive the training and support they need to assess and suggest possible improvements.The authors argue that this absence of opportunity has driven cynicism, apathy, and burnout among physicians. They support a shift in culture and medical education such that students and residents are trained and inspired to act as catalysts who initiate and expedite positive changes. To become catalyst physicians, trainees require tools to partner with patients, staff, and faculty; training in implementing change; and the perception of this work as inherent to the role of the physician.The authors recommend that medical schools consider interprofessional training to be a necessary component of medical education and that future physicians be encouraged to grow in areas outside the "purely clinical" realm. They conclude that both physician catalysts and teamwork are essential for improving care coordination, reducing apathy and burnout, and supporting optimal patient outcomes.

High thermal stability of La 2O 3 and CeO 2-stabilized tetragonal ZrO 2

DOE PAGES

Wang, Shichao; Xie, Hong; Lin, Yuyuan; ...

2016-02-15

Catalyst support materials of tetragonal ZrO 2, stabilized by either La 2O 3 (La 2O 3-ZrO 2) or CeO 2 (CeO 2-ZrO 2), were synthesized under hydrothermal conditions at 200 °C with NH 4OH or tetramethylammonium hydroxide as the mineralizer. From In Situ synchrotron powder X-ray diffraction and small-angle X-ray scattering measurements, the calcined La 2O 3-ZrO 2 and CeO 2-ZrO 2 supports were nonporous nanocrystallites that exhibited rectangular shapes with thermal stability up to 1000 °C in air. These supports had an average size of ~10 nm and a surface area of 59-97 m 2/g. The catalysts Pt/La 2Omore » 3-ZrO 2 and Pt/CeO 2-ZrO 2 were prepared by using atomic layer deposition with varying Pt loadings from 6.3-12.4 wt %. Mono-dispersed Pt nanoparticles of ~3 nm were obtained for these catalysts. As a result, the incorporation of La 2O 3 and CeO 2 into the t-ZrO 2 structure did not affect the nature of the active sites for the Pt/ZrO 2 catalysts for the water-gas-shift (WGS) reaction.« less

In-situ Characterization of Cu/CeO 2 Nanocatalysts during CO 2 Hydrogenation: Morphological Effects of Nanostructured Ceria on the Catalytic Activity

DOE PAGES

Lin, Lili; Yao, Siyu; Liu, Zongyuan; ...

2018-05-28

Here, a combination of time-resolved X-ray diffraction (TR-XRD), ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) was used to carry out an in-situ characterization of Cu/CeO 2 nanocatalysts during the hydrogenation of CO 2. Morphological effects of the ceria supports on the catalytic performances were investigated by examining the behavior of copper/ceria-nanorods (NR) and nanospheres (NS). At atmospheric pressures, the hydrogenation of CO 2 on the copper-ceria catalysts produced mainly CO through the reverse-water gas shift reaction (RWGS) and a negligible amount of methanol. The Cu/CeO 2-NR catalyst displayed the higher activity, which demonstrates thatmore » the RWGS is a structure sensitive reaction. In-situ TR-XRD and AP-XPS characterization showed significant changes in the chemical state of the catalysts under reaction conditions with the copper being fully reduced and a partial Ce 4+ to Ce 3+ transformation occurring. A more effective CO 2 dissociative activation at high temperature and a preferential formation of active bidentate carbonate and formate intermediates over CeO 2(110) terminations are probably the main reasons for the better performance of the Cu/CeO 2-NR catalyst in the RWGS reaction.« less

Characterization of Catalyst Materials for Production of Aerospace Fuels

NASA Technical Reports Server (NTRS)

DeLaRee, Ana B.; Hepp, Aloysius F.

2011-01-01

Due to environmental, economic, and security issues, there is a greater need for cleaner alternative fuels. There will undoubtedly be a shift from crude oil to non-petroleum sources as a feedstock for aviation (and other transportation) fuels. Additionally, efforts are concentrated on reducing costs coupled with fuel production from non-conventional sources. One solution to this issue is Fischer-Tropsch gas-to-liquid technology. Fischer-Tropsch processing of synthesis gas (CO/H2) produces a complex product stream of paraffins, olefins, and oxygenated compounds such as alcohols and aldehydes. The Fisher-Tropsch process can produce a cleaner diesel oil fraction with a high cetane number (typically above 70) without any sulfur or aromatic compounds. This process is most commonly catalyzed by heterogeneous (in this case, silver and platinum) catalysts composed of cobalt supported on alumina or unsupported alloyed iron powders. Physisorption, chemisorptions, scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS) are described to better understand the potential performance of Fischer-Tropsch cobalt on alumina catalysts promoted with silver and platinum. The overall goal is to preferentially produce C8 to C18 paraffin compounds for use as aerospace fuels. Progress towards this goal will eventually be updated and achieved by a more thorough understanding of the characterization of catalyst materials. This work was supported by NASA s Subsonic Fixed Wing and In-situ Resource Utilization projects.

Oxygenates vs. synthesis gas

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

Kamil Klier; Richard G. Herman; Alessandra Beretta

1999-04-01

Methanol synthesis from H{sub 2}/CO has been carried out at 7.6 MPa over zirconia-supported copper catalysts. Catalysts with nominal compositions of 10/90 mol% and 30/70 mol% Cu/ZrO{sub 2} were used in this study. Additionally, a 3 mol% cesium-doped 10/90 catalyst was prepared to study the effect of doping with heavy alkali, and this promoter greatly increased the methanol productivity. The effects of CO{sub 2} addition, water injection, reaction temperature, and H{sub 2}/C0 ratio have been investigated. Both CO{sub 2} addition to the synthesis gas and cesium doping of the catalyst promoted methanol synthesis, while inhibiting the synthesis of dimethyl ether.more » Injection of water, however, was found to slightly suppress methanol and dimethyl ether formation while being converted to CO{sub 2} via the water gas shift reaction over these catalysts. There was no clear correlation between copper surface area and catalyst activity. Surface analysis of the tested samples revealed that copper tended to migrate and enrich the catalyst surface. The concept of employing a double-bed reactor with a pronounced temperature gradient to enhance higher alcohol synthesis was explored, and it was found that utilization of a Cs-promoted Cu/ZnO/Cr{sub 2}O{sub 3} catalyst as a first lower temperature bed and a Cs-promoted ZnO/Cr{sub 2}O{sub 3} catalyst as a second high-temperature bed significantly promoted the productivity of 2-methyl-1-propanol (isobutanol) from H{sub 2}/CO synthesis gas mixtures. While the conversion of CO to C{sub 2+} oxygenates over the double-bed configuration was comparable to that observed over the single Cu-based catalyst, major changes in the product distribution occurred by the coupling to the zinc chromite catalyst; that is, the productivity of the C{sub 1}-C{sub 3} alcohols decreased dramatically, and 2-methyl branched alcohols were selectively formed. The desirable methanol/2-methyl oxygenate molar ratios close to 1 were obtained in the present double-bed system that provides the feedstock for the synthesis of high octane and high cetane ethers, where the isobutanol productivity was as high as 139 g/kg cat/hr. Higher alcohol synthesis has been investigated over a Cs/Cu/ZnO/Cr{sub 2}O{sub 3} catalyst at temperatures higher (up to 703K) than those previously utilized, and no sintering of the catalyst was observed during the short-term testing. However, the higher reaction temperatures led to lower CO conversion levels and lower yield of alcohols, especially of methanol, because of equilibrium limitations. With the double catalyst bed configuration, the effect of pressure in the range of 7.6--12.4 MPa on catalyst activity and selectivity was studied. The upper bed was composed of the copper-based catalyst at 598K, and the lower bed consisted of a copper-free Cs-ZnO/Cr{sub 2}O{sub 3} catalyst at a high temperature of 678K. High pressure was found to increase CO conversion to oxygenated products, although the increase in isobutanol productivity did not keep pace with that of methanol. It was also shown that the Cs/Cu/ZnO/Cr{sub 2}O{sub 3} catalyst could be utilized to advantage as the second-bed catalyst at 613--643K instead of the previously used copper-free Cs-ZnO/ Cr{sub 2}O{sub 3} catalyst at higher temperature, With double Cs/Cu/ZnO/Cr{sub 2}O{sub 3} catalysts, high space time yields of up to 202 g/kg cat/hr, with high selectivity to isobutanol, were achieved.« less

Characterization of LaRhO3 perovskites for dry (CO2) reforming of methane (DRM)

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

Johansson, Ted; Pakhare, Devendra; Haynes, Daniel

2014-01-01

Abstract This work reports on the characterization of LaRhO3 perovskite as a catalyst for dry reforming of methane. The catalyst was studied using CH4-temperature programmed reduction (TPR), H2-TPR, and temperature programmed surface reaction (TPSR), and the changes in the crystal structure of the catalyst due to these treatments were studied by X-ray diffraction (XRD). XRD pattern of the freshly calcined perovskites showed the formation of highly crystalline LaRhO3 and La2O3 phases. H2-TPR of the fresh calcined catalyst showed a shoulder at 342°C and a broad peak at 448°C, suggesting that the reduction of Rh in perovskite occurs in multiple steps.more » XRD pattern of the reduced catalyst suggests complete reduction of the LaRhO3 phase and the formation of metallic Rh and minor amounts of La(OH)3. The CH4-TPR data show qualitatively similar results as H2-TPR, with a shoulder and a broad peak in the same temperature range. Following the H2-TPR up to 950°C, the same batch of catalyst was oxidized by flowing 5 vol. % O2/He up to 500°C and a second H2-TPR (also up to 950°C) was conducted. This second H2-TPR differed significantly from that of the fresh calcined catalyst. The single sharp peak at 163°C in the second H2-TPR suggests a significant change in the catalyst, probably causedby the transformation of about 90 % of the perovskite into Rh/La2O3. This was confirmed by the XRD studies of the catalyst reduced after the oxidation at 500°C. TPSR of the dry reforming reaction on the fresh calcined catalyst showed CO and H2 formation starting at 400°C, with complete consumption of the reactants at 650°C. The uneven consumption of reactants between 400°C and 650°C suggests that reactions other than DRM occur, including reverse water gas shift (RWGS) and the Boudouard reaction (BR), probably as a result of in-situ changes in the catalyst, consistent with the H2-TPR results. TPSR, after a H2-TPR up to 950°C, showed that the dry reforming reaction did not light off until 570°C, which is much higher temperature than the one observed using fresh calcined catalyst. This shows that the uniform sites produced during the 950°C H2-TPR are catalytically less active than those of the fresh calcined catalyst, and that no significant side reactions such as RWGS or the Boudouard reaction occur. This suggests that reduction leads to the formation of a single type of sites which do not catalyze simultaneous side reactions.« less

N-Allyl-N-Sulfonyl Ynamides as Synthetic Precursors to Amidines and Vinylogous Amidines. An Unexpected N-to-C 1,3-Sulfonyl Shift in Nitrile Synthesis

PubMed Central

DeKorver, Kyle A.; Johnson, Whitney L.; Zhang, Yu; Hsung, Richard P.; Dai, Huifang; Deng, Jun; Lohse, Andrew G.; Zhang, Yan-Shi

2011-01-01

A detailed study of amidine synthesis from N-allyl-N-sulfonyl ynamides is described here. Mechanistically, this is a fascinating reaction consisting of diverging pathways that could lead to deallylation or allyl transfer depending upon the oxidation state of palladium catalysts, the nucleophilicity of amines, and the nature of the ligands. It essentially constitutes a Pd(0)-catalyzed aza-Claisen rearrangement of N-allyl ynamides, which can also be accomplished thermally. An observation of N-to-C 1,3-sulfonyl shift was made when examining these aza-Claisen rearrangements thermally. This represents a useful approach to nitrile synthesis. While attempts to render this 1,3-sulfonyl shift stereoselective failed, we uncovered another set of tandem sigmatropic rearrangements, leading to vinyl imidate formation. Collectively, this work showcases the rich array of chemistry one can discover using these ynamides. PMID:21563776

Secondary Confinement of Water Observed in Eutectic Melting of Aqueous Salt Systems in Nanopores.

PubMed

Meissner, Jens; Prause, Albert; Findenegg, Gerhard H

2016-05-19

Freezing and melting of aqueous solutions of alkali halides confined in the cylindrical nanopores of MCM-41 and SBA-15 silica was probed by differential scanning calorimetry (DSC). We find that the confinement-induced shift of the eutectic temperature in the pores can be significantly greater than the shift of the melting temperature of pure water. Greatest shifts of the eutectic temperature are found for salts that crystallize as oligohydrates at the eutectic point. This behavior is explained by the larger fraction of pore volume occupied by salt hydrates as compared to anhydrous salts, on the assumption that precipitated salt constitutes an additional confinement for ice/water in the pores. A model based on this secondary confinement effect gives a good representation of the experimental data. Salt-specific secondary confinement may play a role in a variety of fields, from salt-impregnated advanced adsorbents and catalysts to the thermal weathering of building materials.

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

NASA Astrophysics Data System (ADS)

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

2009-03-01

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

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

Yao, Siyu; Zhang, Xiao; Zhou, Wu

Here, the water-gas shift (WGS) reaction (where carbon monoxide plus water yields dihydrogen and carbon dioxide) is an essential process for hydrogen generation and carbon monoxide removal in various energy-related chemical operations. This equilibrium-limited reaction is favored at a low working temperature. Potential application in fuel cells also requires a WGS catalyst to be highly active, stable, and energy-efficient and to match the working temperature of on-site hydrogen generation and consumption units. We synthesized layered gold (Au) clusters on a molybdenum carbide (α-MoC) substrate to create an interfacial catalyst system for the ultralow-temperature WGS reaction. Water was activated over α-MoCatmore » 303 kelvin, whereas carbon monoxide adsorbed on adjacent Au sites was apt to react with surface hydroxyl groups formed from water splitting, leading to a high WGS activity at low temperatures.« less

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

Habitat associations of species show consistent but weak responses to climate

PubMed Central

Suggitt, Andrew J.; Stefanescu, Constantí; Páramo, Ferran; Oliver, Tom; Anderson, Barbara J.; Hill, Jane K.; Roy, David B.; Brereton, Tom; Thomas, Chris D.

2012-01-01

Different vegetation types can generate variation in microclimates at local scales, potentially buffering species from adverse climates. To determine if species could respond to such microclimates under climatic warming, we evaluated whether ectothermic species (butterflies) can exploit favourable microclimates and alter their use of different habitats in response to year-to-year variation in climate. In both relatively cold (Britain) and warm (Catalonia) regions of their geographical ranges, most species shifted into cooler, closed habitats (e.g. woodland) in hot years, and into warmer, open habitats (e.g. grassland) in cooler years. Additionally, three-quarters of species occurred in closed habitats more frequently in the warm region than in the cool region. Thus, species shift their local distributions and alter their habitat associations to exploit favourable microclimates, although the magnitude of the shift (approx. 1.3% of individuals from open to shade, per degree Celsius) is unlikely to buffer species from impacts of regional climate warming. PMID:22491762

A tunable comb filter using single-mode/multimode/polarization-maintaining-fiber-based Sagnac fiber loop

NASA Astrophysics Data System (ADS)

Ruan, Juan; Zhang, Wei-Gang; Zhang, Hao; Geng, Peng-Cheng; Bai, Zhi-Yong

2013-06-01

A novel tunable comb filter composed of a single-mode/multimode/polarization-maintaining-fiber-based Sagnac fiber loop is proposed and experimentally demonstrated. The filter tunability is achieved by rotating the polarization controller. The spectral shift is dependent on rotation direction and the position of the polarization controller. In addition, the adjustable range achieved by rotating the half-wave-plate polarization controller is twice higher than that of the quarter-wave-plate one.

Micro-Membrane Electrode Assembly Design to Precisely Measure the in Situ Activity of Oxygen Reduction Reaction Electrocatalysts for PEMFC.

PubMed

Long, Zhi; Li, Yankai; Deng, Guangrong; Liu, Changpeng; Ge, Junjie; Ma, Shuhua; Xing, Wei

2017-06-20

An in situ micro-MEA technique, which could precisely measure the performance of ORR electrocatalyst using Nafion as electrolyte, was designed and compared with regular thin-film rotating-disk electrode (TFRDE) (0.1 M HClO 4 ) and normal in situ membrane electrode assembly (MEA) tests. Compared to the traditional TFRDE method, the micro-MEA technique makes the acquisition of catalysts' behavior at low potential values easily achieved without being limited by the solubility of O 2 in water. At the same time, it successfully mimics the structure of regular MEAs and obtains similar results to a regular MEA, thus providing a new technique to simply measure the electrode activity without being bothered by complicated fabrication of regular MEA. In order to further understand the importance of in situ measurement, Fe-N-C as a typical oxygen reduction reaction (ORR) free-Pt catalyst was evaluated by TFRDE and micro-MEA. The results show that the half wave potential of Fe-N-C only shifted negatively by -135 mV in comparison with state-of-the-art Pt/C catalysts from TFRDE tests. However, the active site density, mass transfer of O 2 , and the proton transfer conductivity are found to strongly influence the catalyst activity in the micro-MEA, thereby resulting in a much lower limiting current density than Pt/C (8.7 times lower). Hence, it is suggested that the micro-MEA is better in evaluating the in situ ORR performance, where the catalysts are characterized more thoroughly in terms of intrinsic activity, active site density, proton transfer, and mass transfer properties.

Combustion behaviors and kinetics of sewage sludge blended with pulverized coal: With and without catalysts.

PubMed

Wang, Zhiqiang; Hong, Chen; Xing, Yi; Li, Yifei; Feng, Lihui; Jia, Mengmeng

2018-04-01

The combustion behaviors of sewage sludge (SS), pulverized coal (PC), and their blends were studied using a thermogravimetric analyzer. The effect of the mass ratio of SS to PC on the co-combustion characteristics was analyzed. The experiments showed that the ignition performance of the blends improved significantly as the mass percentage of SS increased, but its combustion intensity decreased. The burnout temperature (T b ) and comprehensive combustibility index (S) of the blends were almost unchanged when the mass percentage of SS was less than 10%. However, a high mass percentage of SS (>10%) resulted in a great increase in T b and a notable decrease in S. Subsequently, the effects of different catalysts (CaO, CeO 2 , MnO 2 , and Fe 2 O 3 ) on the combustion characteristics and activation energy of the SS/PC blend were investigated. The four catalysts promoted the release and combustion of volatile matters in the blended fuels and shifted their combustion profiles to a low temperature. In addition, their peak separating tendencies were obvious at 350-550 C, resulting in high peak widths. All the catalysts improved combustion activity of the blended fuel and accelerated fixed carbon combustion, which decreased the ignition temperature and burnout temperature of the fuels. CeO 2 had the best catalytic effects in terms of the comprehensive combustion performance and activation energy, followed closely by Fe 2 O 3 . However, the rare-earth compounds are expensive to be applied in the catalytic combustion process of SS/PC blend at present. Based on both catalytic effects and economy, Fe 2 O 3 was potentially an optimal option for catalytic combustion among the tested catalysts. Copyright © 2018 Elsevier Ltd. All rights reserved.

Novel Fast Pyrolysis/Catalytic Technology for the Production of Stable Upgraded Liquids

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

Oyama, Ted; Agblevor, Foster; Battaglia, Francine

The objective of the proposed research is the demonstration and development of a novel biomass pyrolysis technology for the production of a stable bio-oil. The approach is to carry out catalytic hydrodeoxygenation (HDO) and upgrading together with pyrolysis in a single fluidized bed reactor with a unique two-level design that permits the physical separation of the two processes. The hydrogen required for the HDO will be generated in the catalytic section by the water-gas shift reaction employing recycled CO produced from the pyrolysis reaction itself. Thus, the use of a reactive recycle stream is another innovation in this technology. Themore » catalysts will be designed in collaboration with BASF Catalysts LLC (formerly Engelhard Corporation), a leader in the manufacture of attrition-resistant cracking catalysts. The proposed work will include reactor modeling with state-of-the-art computational fluid dynamics in a supercomputer, and advanced kinetic analysis for optimization of bio-oil production. The stability of the bio-oil will be determined by viscosity, oxygen content, and acidity determinations in real and accelerated measurements. A multi-faceted team has been assembled to handle laboratory demonstration studies and computational analysis for optimization and scaleup.« less

Fuel processing in integrated micro-structured heat-exchanger reactors

NASA Astrophysics Data System (ADS)

Kolb, G.; Schürer, J.; Tiemann, D.; Wichert, M.; Zapf, R.; Hessel, V.; Löwe, H.

Micro-structured fuel processors are under development at IMM for different fuels such as methanol, ethanol, propane/butane (LPG), gasoline and diesel. The target application are mobile, portable and small scale stationary auxiliary power units (APU) based upon fuel cell technology. The key feature of the systems is an integrated plate heat-exchanger technology which allows for the thermal integration of several functions in a single device. Steam reforming may be coupled with catalytic combustion in separate flow paths of a heat-exchanger. Reactors and complete fuel processors are tested up to the size range of 5 kW power output of a corresponding fuel cell. On top of reactor and system prototyping and testing, catalyst coatings are under development at IMM for numerous reactions such as steam reforming of LPG, ethanol and methanol, catalytic combustion of LPG and methanol, and for CO clean-up reactions, namely water-gas shift, methanation and the preferential oxidation of carbon monoxide. These catalysts are investigated in specially developed testing reactors. In selected cases 1000 h stability testing is performed on catalyst coatings at weight hourly space velocities, which are sufficiently high to meet the demands of future fuel processing reactors.

Transition-Metal-Free Synthesis of 1,3-Butadiene-Containing π-Conjugated Polymers.

PubMed

Cai, Xuediao; Liu, Yating; Lu, Tian; Yang, Rui; Luo, Chuxin; Zhang, Qi; Chai, Yonghai

2016-12-01

This work describes the synthesis of π-conjugated polymers possessing arylene and 1,3-butadiene alternating units in the main chain by the reaction of α,β-unsaturated ester/nitrile containing γ-H with aromatic/heteroaromatic aldehyde compound. By using 4-(4-formylphenyl)-2-butylene acid ethyl ester as a model monomer, the different polymerization conditions, including catalyst, catalyst amount, and solvent, are optimized. The polymerization of 4-(4-formylphenyl)-2-butylene acid ethyl ester is carried out by refluxing in ethanol for 72 h with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as a catalyst to give a 1,3-butadiene-containing π-conjugated polymer, poly(phenylene-1,3-butadiene), in 84.3% yield with M¯n and M¯w/M¯n (PDI) estimated as 6172 and 1.65, respectively. Based on this new methodology, a series of π-conjugated polymers containing 1,3-butadiene units with different substituents are obtained in high yields. A possible mechanism is proposed for the polymerization through a six-membered ring transition state and then a 1,5-H shift intermediate. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

In situ and theoretical studies for the dissociation of water on an active Ni/CeO2 catalyst: importance of strong metal-support interactions for the cleavage of O-H bonds.

PubMed

Carrasco, Javier; López-Durán, David; Liu, Zongyuan; Duchoň, Tomáš; Evans, Jaime; Senanayake, Sanjaya D; Crumlin, Ethan J; Matolín, Vladimir; Rodríguez, José A; Ganduglia-Pirovano, M Verónica

2015-03-23

Water dissociation is crucial in many catalytic reactions on oxide-supported transition-metal catalysts. Supported by experimental and density-functional theory results, the effect of the support on OH bond cleavage activity is elucidated for nickel/ceria systems. Ambient-pressure O 1s photoemission spectra at low Ni loadings on CeO2 (111) reveal a substantially larger amount of OH groups as compared to the bare support. Computed activation energy barriers for water dissociation show an enhanced reactivity of Ni adatoms on CeO2 (111) compared with pyramidal Ni4 particles with one Ni atom not in contact with the support, and extended Ni(111) surfaces. At the origin of this support effect is the ability of ceria to stabilize oxidized Ni(2+) species by accommodating electrons in localized f-states. The fast dissociation of water on Ni/CeO2 has a dramatic effect on the activity and stability of this system as a catalyst for the water-gas shift and ethanol steam reforming reactions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Operando Synchrotron X-ray Powder Diffraction and Modulated-Excitation Infrared Spectroscopy Elucidate the CO2 Promotion on a Commercial Methanol Synthesis Catalyst.

PubMed

Martin, Oliver; Mondelli, Cecilia; Cervellino, Antonio; Ferri, Davide; Curulla-Ferré, Daniel; Pérez-Ramírez, Javier

2016-09-05

Optimal amounts of CO2 are added to syngas to boost the methanol synthesis rate on Cu-ZnO-Al2 O3 in the industrial process. The reason for CO2 promotion is not sufficiently understood at the particle level due to the catalyst complexity and the high demands of characterization under true reaction conditions. Herein, we applied operando synchrotron X-ray powder diffraction and modulated-excitation infrared spectroscopy on a commercial catalyst to gain insights into its morphology and surface chemistry. These studies unveiled that Cu and ZnO agglomerate and ZnO particles flatten under CO/H2 and/or CO2 /H2 . Under the optimal CO/CO2 /H2 mixture, sintering is prevented and ZnO crystals adopt an elongated shape due to the minimal presence of the H2 O byproduct, enhancing the water-gas shift activity and thus the methanol production. Our results provide a rationale to the CO2 promotion emphasizing the importance of advanced analytical methods to establish structure-performance relations in heterogeneous catalysis. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Molecular interactions between carbon nanotubes and ammonium ionic liquids and their catalysis properties

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

Attri, Pankaj, E-mail: chem.pankaj@gmail.com; Bhatia, Rohit; Arora, Bharti

2014-10-15

Highlights: • We report interactions between multi-walled carbon nanotubes and ionic liquids. • Triethylammonium hydrogen phosphate ionic liquids are studied. • Raman spectroscopy is used to study interactions. • Morphological studies were carried out using scanning electron microscopy. • Bucky gel was used as catalyst for Michael reactions. - Abstract: A new catalytic method has been developed for the synthesis of aza/thia-Michael addition reactions of amines/thiols, which provide higher product yields. This catalyst is a combination of multi-walled carbon nanotubes (MWCNT) with triethylammonium hydrogen phosphate (TEAP) ionic liquid (IL), commonly referred to as bucky gel. In order to gain insightmore » into the interactions involved between IL and MWCNT, we utilised Raman spectroscopy for our analysis. The interactions between MWCNT with TEAP were clearly evidenced by the increasing intensity ratios and spectral shift in the wavelength for the Raman D and G bands of MWCNT. The morphological studies of the resulting composite materials of TEAP and MWCNT (bucky gel) were carried out using scanning electron microscopy (SEM). The key advantage of using bucky gel as a catalyst is that higher product yield is obtained in reduced reaction time for Michael reactions.« less

In-situ and theoretical studies for the dissociation of water on an active Ni/CeO₂ catalyst: Importance of strong metal-support interactions for the cleavage of O-H bonds

DOE PAGES

Carrasco, Javier; Rodriguez, Jose A.; Lopez-Duran, David; ...

2015-03-23

Water dissociation is crucial in many catalytic reactions on oxide-supported transition-metal catalysts. Here, supported by experimental and density-functional theory results, we elucidate the effect of the support on O-H bond cleavage activity for nickel/ceria systems. Ambient-pressure O1s photoemission spectra at low Ni loadings on CeO₂(111) reveal a substantially larger amount of OH groups as compared to the bare support. Our computed activation energy barriers for water dissociation show an enhanced reactivity of Ni adatoms on CeO₂(111) compared with pyramidal Ni₄ particles with one Ni atom not in contact with the support, and extended Ni(111) surfaces. At the origin of thismore » support effect is the ability of ceria to stabilize oxidized Ni²⁺ species by accommodating electrons in localized f-states. The fast dissociation of water on Ni/CeO₂ has a dramatic effect on the activity and stability of this system as a catalyst for the water-gas shift and ethanol steam reforming reactions.« less

Method for simultaneous recovery of hydrogen from water and from hydrocarbons

DOEpatents

Willms, R. Scott

1996-01-01

Method for simultaneous recovery of hydrogen and hydrogen isotopes from water and from hydrocarbons. A palladium membrane, when utilized in cooperation with a nickel catalyst in a reactor, has been found to drive reactions such as water gas shift, steam reforming and methane cracking to substantial completion by removing the product hydrogen from the reacting mixture. In addition, ultrapure hydrogen is produced, thereby eliminating the need for an additional processing step.

U. S. (United States) Air Force Fuel Cell Application Analysis.

DTIC Science & Technology

1982-01-01

Desulfurizer and shift cata- lyst temperatures are maintained by controlling the amount of gas entering or by-passing the external water vaporizer. If...rich gas . The sul- fur content of the desulfurized fuel gas must be less than 1 ppm. Reforming takes place in a nickel catalyst bed, operating at... Control Supplemental Firing Fuel Cell Temperature Recirculation Air Temperature Control via Cooler Fan Speed Exhaust Gas Water Load Following damper

Characteristics of hydrogen produced by partial oxidation and auto-thermal reforming in a small methanol reformer

NASA Astrophysics Data System (ADS)

Horng, Rong-Fang; Chou, Huann-Ming; Lee, Chiou-Hwang; Tsai, Hsien-Te

This paper investigates experimentally, the transient characteristics of a small methanol reformer using partial oxidation (POX) and auto-thermal reforming (ATR) for fuel cell applications. The parameters varied were heating temperature, methanol supply rate, steady mode shifting temperature, O 2/C (O 2/CH 3OH) and S/C (H 2O/CH 3OH) molar ratios with the main aim of promoting a rapid response and a high flow rate of hydrogen. The experiments showed that a high steady mode shifting temperature resulted in a faster temperature rise at the catalyst outlet and vice versa and that a low steady mode shifting temperature resulted in a lower final hydrogen concentration. However, when the mode shifting temperature was too high, the hydrogen production response was not necessarily improved. It was subsequently shown that the optimum steady mode shifting temperature for this experimental set-up was approximately 75 °C. Further, the hydrogen concentration produced by the auto-thermal process was as high as 49.12% and the volume flow rate up to 23.0 L min -1 compared to 40.0% and 20.5 L min -1 produced by partial oxidation.

A diesel fuel processor for fuel-cell-based auxiliary power unit applications

NASA Astrophysics Data System (ADS)

Samsun, Remzi Can; Krekel, Daniel; Pasel, Joachim; Prawitz, Matthias; Peters, Ralf; Stolten, Detlef

2017-07-01

Producing a hydrogen-rich gas from diesel fuel enables the efficient generation of electricity in a fuel-cell-based auxiliary power unit. In recent years, significant progress has been achieved in diesel reforming. One issue encountered is the stable operation of water-gas shift reactors with real reformates. A new fuel processor is developed using a commercial shift catalyst. The system is operated using optimized start-up and shut-down strategies. Experiments with diesel and kerosene fuels show slight performance drops in the shift reactor during continuous operation for 100 h. CO concentrations much lower than the target value are achieved during system operation in auxiliary power unit mode at partial loads of up to 60%. The regeneration leads to full recovery of the shift activity. Finally, a new operation strategy is developed whereby the gas hourly space velocity of the shift stages is re-designed. This strategy is validated using different diesel and kerosene fuels, showing a maximum CO concentration of 1.5% at the fuel processor outlet under extreme conditions, which can be tolerated by a high-temperature PEFC. The proposed operation strategy solves the issue of strong performance drop in the shift reactor and makes this technology available for reducing emissions in the transportation sector.

Electric field changes on Au nanoparticles on semiconductor supports--the molecular voltmeter and other methods to observe adsorbate-induced charge-transfer effects in Au/TiO2 nanocatalysts.

PubMed

McEntee, Monica; Stevanovic, Ana; Tang, Wenjie; Neurock, Matthew; Yates, John T

2015-02-11

Infrared (IR) studies of Au/TiO2 catalyst particles indicate that charge transfer from van der Waals-bound donor or acceptor molecules on TiO2 to or from Au occurs via transport of charge carriers in the semiconductor TiO2 support. The ΔνCO on Au is shown to be proportional to the polarizability of the TiO2 support fully covered with donor or acceptor molecules, producing a proportional frequency shift in νCO. Charge transfer through TiO2 is associated with the population of electron trap sites in the bandgap of TiO2 and can be independently followed by changes in photoluminescence intensity and by shifts in the broad IR absorbance region for electron trap sites, which is also proportional to the polarizability of donors by IR excitation. Density functional theory calculations show that electron transfer from the donor molecules to TiO2 and to supported Au particles produces a negative charge on the Au, whereas the transfer from the Au particles to the TiO2 support into acceptor molecules results in a positive charge on the Au. These changes along with the magnitudes of the shifts are consistent with the Stark effect. A number of experiments show that the ∼3 nm Au particles act as "molecular voltmeters" in influencing ΔνCO. Insulator particles, such as SiO2, do not display electron-transfer effects to Au particles on their surface. These studies are preliminary to doping studies of semiconductor-oxide particles by metal ions which modify Lewis acid/base oxide properties and possibly strongly modify the electron-transfer and catalytic activity of supported metal catalyst particles.

Combined far infrared RAIRS and XPS studies of TiCl 4 adsorption and reaction on Mg films

NASA Astrophysics Data System (ADS)

Pilling, M. J.; Fonseca, A. Amieiro; Cousins, M. J.; Waugh, K. C.; Surman, M.; Gardner, P.

2005-08-01

In recent years there has been an increase in interest in the study of model Ziegler-Natta catalysts used for the polymerisation of ethene and propene. Particular attention has focused on catalysts consisting of TiCl 4 on activated MgCl 2 accompanied by a co-catalyst, usually triethylaluminium (AlEt 3). As part of a wider project on the characterisation of model Ziegler-Natta catalysts we have investigated the interaction of TiCl 4 with metallic Mg films grown on a Au surface using X-ray photoelectron spectroscopy (XPS) and far infrared reflection absorption infrared spectroscopy. Somewhat surprisingly, the infrared spectra show little variation as a function of exposure to TiCl 4. A very broad asymmetric vibrational band grows in with maximum intensity at 382 cm -1. Three prominent low frequency shoulders are observed at approximately 360, 320, and 260 cm -1. For monolayer coverages of Mg the main band at 382 cm -1 is narrower, less asymmetric and accompanied by a prominent shoulder at 398 cm -1, which increases with increasing exposure to TiCl 4. TiCl 4 exposure in the presence of 5 × 10 -8 Torr of ethyl benzoate results in a change in line shape with low frequency broadening and a small shift in the frequency of the band. These spectra are discussed in the light of the possible constituent species making up the surface layer.

Field-emission property of self-purification SiC/SiOx coaxial nanowires synthesized via direct microwave irradiation using iron-containing catalyst

NASA Astrophysics Data System (ADS)

Zhou, Qing; Yu, Yongzhi; Huang, Shan; Meng, Jiang; Wang, Jigang

2017-07-01

SiC/SiOx coaxial nanowires were rapidly synthesized via direct microwave irradiation in low vacuum atmosphere. During the preparation process, only graphite, silicon, silicon dioxide powders were used as raw materials and iron-containing substance was employed as catalyst. Comprehensive characterizations were employed to investigate the microstructure of the products. The results showed that a great quantity of coaxial nanowires with uniform sizes and high aspect ratio had been successfully achieved. The coaxial nanowires consist of a silicon oxide (SiOx) shell and a β-phase silicon carbide (β-SiC) core that exhibited in special tube brush like. In additional, nearly all the products were achieved in the statement of pure SiC/SiOx coaxial nanowires without the existence of metallic catalyst, indicating that the self-removal of iron (Fe) catalyst should be occurred during the synthesis process. Photoluminescence (PL) spectral analysis result indicated that such novel SiC/SiOx coaxial nanowires exhibited significant blue-shift. Besides, the measurement results of field-emission (FE) demonstrated that the SiC/SiOx coaxial nanowires had ultralow turn-on field and threshold field with values of 0.2 and 2.1 V/μm, respectively. The hetero-junction structure formed between SiOx shell and SiC core, lots of emission sites, as well as clear tips of the nanowires were applied to explain the excellent FE properties.[Figure not available: see fulltext.

Syngas Production from CO2 Reforming and CO2-steam Reforming of Methane over Ni/Ce-SBA-15 Catalyst

NASA Astrophysics Data System (ADS)

Tan, J. S.; Danh, H. T.; Singh, S.; Truong, Q. D.; Setiabudi, H. D.; Vo, D.-V. N.

2017-06-01

This study compares the catalytic performance of mesoporous 10 Ni/Ce-SBA-15 catalyst for CO2 reforming and CO2-steam reforming of methane reactions in syngas production. The catalytic performance of 10 Ni/Ce-SBA-15 catalyst for CO2 reforming and CO2-steam reforming of methane was evaluated in a temperature-controlled tubular fixed-bed reactor at stoichiometric feed composition, 1023 K and atmospheric pressure for 12 h on-stream with gas hourly space velocity (GHSV) of 36 L gcat -1 h-1. The 10 Ni/Ce-SBA-15 catalyst possessed a high specific BET surface area and average pore volume of 595.04 m2 g-1. The XRD measurement revealed the presence of NiO phase with crystallite dimension of about 13.60 nm whilst H2-TPR result indicates that NiO phase was completely reduced to metallic Ni0 phase at temperature beyond 800 K and the reduction temperature relied on different degrees of metal-support interaction associated with the location and size of NiO particles. The catalytic reactivity was significantly enhanced with increasing H2O/CO2 feed ratio. Interestingly, the H2/CO ratio for CO2-steam reforming of methane varied between 1 and 3 indicated the occurrence of parallel reactions, i.e., CH4 steam reforming giving a H2/CO of 3 whilst reverse water-gas shift (RWGS) reaction consuming H2 to produce CO gaseous product.

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.

Apparatus for converting hydrocarbon fuel into hydrogen gas and carbon dioxide

DOEpatents

Clawson, Lawrence G.; Mitchell, William L.; Bentley, Jeffrey M.; Thijssen, Johannes H. J.

2001-01-01

A hydrocarbon fuel reformer (200) is disclosed suitable for producing synthesis hydrogen gas from reactions with hydrocarbons fuels, oxygen, and steam. The reformer (200) comprises first and second tubes (208,218). The first tube (208) includes a first catalyst (214) and receives a first mixture of steam and a first fuel. The second tube (218) is annularly disposed about the first tube (208) and receives a second mixture of an oxygen-containing gas and a second fuel. In one embodiment, a third tube (224) is annularly disposed about the second tube (218) and receives a first reaction reformate from the first tube (208) and a second reaction reformate from the second tube (218). A catalyst reforming zone (260) annularly disposed about the third tube (224) may be provided to subject reformate constituents to a shift reaction. In another embodiment, a fractionator is provided to distill first and second fuels from a fuel supply source.

Transition-Metal Nitride Core@Noble-Metal Shell Nanoparticles as Highly CO Tolerant Catalysts

DOE PAGES

Garg, Aaron; Milina, Maria; Ball, Madelyn; ...

2017-05-25

Core–shell architectures offer an effective way to tune and enhance the properties of noble-metal catalysts. Herein, we demonstrate the synthesis of Pt shell on titanium tungsten nitride core nanoparticles (Pt/TiWN) by high temperature ammonia nitridation of a parent core–shell carbide material (Pt/TiWC). X-ray photoelectron spectroscopy revealed significant core-level shifts for Pt shells supported on TiWN cores, corresponding to increased stabilization of the Pt valence d-states. The modulation of the electronic structure of the Pt shell by the nitride core translated into enhanced CO tolerance during hydrogen electrooxidation in the presence of CO. In conclusion, the ability to control shell coveragemore » and vary the heterometallic composition of the shell and nitride core opens up attractive opportunities to synthesize a broad range of new materials with tunable catalytic properties.« less

Model systems in heterogeneous catalysis: towards the design and understanding of structure and electronic properties.

PubMed

Pan, Q; Li, L; Shaikhutdinov, S; Fujimori, Y; Hollerer, M; Sterrer, M; Freund, H-J

2018-05-29

We discuss in this paper two case studies related to nano-particle catalyst systems. One concerns a model system for the Cr/SiO2 Phillips catalyst for ethylene polymerization and here we present XPS data to complement the previously published TPD, IRAS and reactivity studies to elucidate the electronic structure of the system in some detail. The second case study provides additional information on Au nano-particles supported on ultrathin MgO(100)/Ag(100) films where we had observed a specific activity of the particle's rim at the metal-oxide interface with respect to CO2 activation and oxalate formation, obviously connected to electron transfer through the MgO film from the metal substrate underneath. Here we present XPS and Auger data, which allows detailed analysis of the observed chemical shifts. This analysis corroborates previous findings deduced via STM.

NASA Redox Project status summary

NASA Technical Reports Server (NTRS)

Hagedorn, N. H.

1983-01-01

This report is a summary of the results of the Redox Project effort during Cy 1982. It was presented at the Fifth U.S. Department of Energy Battery and Electrochemical Contractors Conference, Arlington, Va., Dec. 7-9, 1982. The major development during 1982 was the shift from Redox system operation at 25 C with unmixed reactants to operation at 65 C with mixed reactants. This change has made possible a two- or three-fold increase in operating current density, to about 65 mA/sq cm, and an increase in reactant utilization from 40% to about 90%. Both of these improvements will lead to significant system cost reductions. Contract studies have indicated that Redox reactant costs also will be moderate. A new catalyst for the chromuim electrode offers all the advantages of the conventional gold-lead catalyst while being easier to apply and more forgiving in use.

Transition-Metal Nitride Core@Noble-Metal Shell Nanoparticles as Highly CO Tolerant Catalysts

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

Garg, Aaron; Milina, Maria; Ball, Madelyn

Core–shell architectures offer an effective way to tune and enhance the properties of noble-metal catalysts. Herein, we demonstrate the synthesis of Pt shell on titanium tungsten nitride core nanoparticles (Pt/TiWN) by high temperature ammonia nitridation of a parent core–shell carbide material (Pt/TiWC). X-ray photoelectron spectroscopy revealed significant core-level shifts for Pt shells supported on TiWN cores, corresponding to increased stabilization of the Pt valence d-states. The modulation of the electronic structure of the Pt shell by the nitride core translated into enhanced CO tolerance during hydrogen electrooxidation in the presence of CO. In conclusion, the ability to control shell coveragemore » and vary the heterometallic composition of the shell and nitride core opens up attractive opportunities to synthesize a broad range of new materials with tunable catalytic properties.« less

Advanced direct coal liquefaction concepts. Quarterly report, January 1, 1993--March 31, 1993

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

Berger, D.J.; Parker, R.J.; Simpson, P.L.

1993-07-01

Five barrels of a Wilsonville process derived solvent (V-1074) from Black Thunder coal were obtained. This material boils within the preferred gas oil range, is more aromatic than previous solvents, and will therefore be used for the bench unit studies. Several repeat runs were performed in the autoclave to confirm the results of the matrix study. In addition, runs were carried out with different catalysts, with agglomerates and with the V-1074 solvent. The results of the autoclave runs were analyzed with respect to coal conversion, CO conversion, oil yield, hydrogen consumption and oxygen removal. It was concluded that the bestmore » operating conditions for the first stage operation was a temperature of at least 390{degrees}C, residence time of at least 30 minutes, cold CO pressure of at least 600 psig and potassium carbonate catalyst (2% wt on total feed). The data also indicated however, that the coal conversion goes through a maximum, and too high a severity leads to retrograde reaction and lower coal solubilization. The scope for increasing temperature and time is therefore limited. Petrographic examination of the THF insoluble resids from the autoclave program indicated a maximum coal conversion of about 90% for Black Thunder coal. The bench unit construction was also essentially completed and the bench unit program to be carded out in the next twelve months was defined.« less

Symptoms of fatigue and coping strategies in maritime pilotage.

PubMed

Chambers, Timothy P; Main, Luana C

2015-01-01

Little is known regarding the symptoms of fatigue that maritime pilots experience during shift work. Moreover, the strategies these individuals use to cope with the onset of fatigue are also unknown. The current study explored the symptoms of fatigue and coping strategies experienced by maritime pilots when on-shift. Fifty maritime pilots were recruited via an advertisement in the national association's quarterly newsletter (Mage = 51.42; SD = 9.81). Participants responded to a modified version of the questionnaire used with aviation pilots that assessed overall fatigue, and the symptoms pilots associated with fatigue on duty. Methods pilots used to cope with fatigue before shift and when on the bridge were also assessed. There were significant effects for pilot vitality on 4 categories of fatigue: cognitive dysfunction; emotional disturbance; mean physical effects; and sleepiness. There were no significant effects for vitality on any of the self-reported coping strategy factors. The findings indicated that maritime pilots experience a variety of physical, behavioural, and cognitive fatigue symptoms when on shift. Some of these symptoms are similar to those reported by aviation pilots. However, unlike aviation pilots, maritime pilots reported utilising self-sufficient coping strategies to deal with the experience of fatigue.

PRESSURE SHIFT AND GRAVITATIONAL REDSHIFT OF BALMER LINES IN WHITE DWARFS: REDISCUSSION

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

Halenka, Jacek; Olchawa, Wieslaw; Madej, Jerzy

2015-08-01

The Stark-induced shift and asymmetry, the so-called pressure shift (PS) of H{sub α} and H{sub β} Balmer lines in spectra of DA white dwarfs (WDs), have been examined in detail as masking effects in measurements of the gravitational redshift in WDs. The results are compared with our earlier ones from a quarter of a century ago. In these earlier papers, the standard, symmetrical Stark line profiles, as a dominant constituent of the Balmer line profiles but shifted as a whole by the PS effect, were applied to all spectrally active layers of the WD atmosphere. At present, in each ofmore » the WD layers, the Stark line profiles (especially of H{sub β}) are inherently asymmetrical and shifted due to the effects of strong inhomogeneity of the perturbing fields in plasma. To calculate the Stark line profiles in successive layers of the WD atmosphere we used the modified Full Computer Simulation Method, able to take adequately into account the complexity of local elementary quantum processes in plasma. In the case of the H{sub α} line, the present value of Stark-induced shift of the synthetic H{sub α} line profile is about half the previous one and it is negligible in comparison with the gravitational redshift. In the case of the H{sub β} line, the present value of Stark-induced shift of the synthetic H{sub β} line profile is about twice the previous one. The source of this extra shift is the asymmetry of H{sub β} peaks.« less

Method of operating a neutronic reactor

DOEpatents

Woods, Wallace K.

1976-05-25

1. A method of operating a reactor having an active portion of a given length between a charging end and a discharging end, a first end region of the reactor extending from the charging end for one-quarter to one-third of said given length, a second end region extending from the discharging end for one-quarter to one-third of said given length, and a middle region extending between said end regions, said method comprising the steps of inserting end to end in the active region through the charging end a first group of bodies filling the middle region and a second group of bodies filling the first end region, irradiating the first and second groups of bodies while in the middle and first end regions, removing the first group from the reactor through the second end region, shifting the second group through the middle region to the second end region, inserting new first and second groups of bodies through the charging face into the middle and first end regions of the reactor, respectively, and irradiating the original second group and the new first and second groups while in the second end, middle, and first end regions, respectively, removing the original second group and the new first group from the reactor through the second end region, shifting the new second group through the middle region to the second end region, and irradiating the new second group again, whereby the first groups of bodies are irradiated only once and the second groups are irradiated twice.

Iridium-catalyzed direct tetraborylation of perylene bisimides.

PubMed

Teraoka, Takuro; Hiroto, Satoru; Shinokubo, Hiroshi

2011-05-20

Treatment of perylene bisimides (PBIs) with bis(pinacolato)diboron in the presence of an iridium catalyst provides tetraborylated PBIs at 2,5,8,11-positions in good yields with perfect regioselectivity. The planar structure of the perylene core has been confirmed by X-ray diffraction analysis. Oxidation of tetraborylated PBI with hydroxylamine hydrochloride affords tetrahydroxy PBI in excellent yield, which exhibits a substantially blue-shifted absorption spectrum due to an intramolecular hydrogenbonding interaction between carbonyl and hydroxy groups.

Polydopamine-Coated Manganese Complex/Graphene Nanocomposite for Enhanced Electrocatalytic Activity Towards Oxygen Reduction.

PubMed

Parnell, Charlette M; Chhetri, Bijay; Brandt, Andrew; Watanabe, Fumiya; Nima, Zeid A; Mudalige, Thilak K; Biris, Alexandru S; Ghosh, Anindya

2016-08-16

Platinum electrodes are commonly used electrocatalysts for oxygen reduction reactions (ORR) in fuel cells. However, this material is not economical due to its high cost and scarcity. We prepared an Mn(III) catalyst supported on graphene and further coated with polydopamine, resulting in superior ORR activity compared to the uncoated PDA structures. During ORR, a peak potential at 0.433 V was recorded, which is a significant shift compared to the uncoated material's -0.303 V (both versus SHE). All the materials reduced oxygen in a wide pH range via a four-electron pathway. Rotating disk electrode and rotating ring disk electrode studies of the polydopamine-coated material revealed ORR occurring via 4.14 and 4.00 electrons, respectively. A rate constant of 6.33 × 10(6) mol(-1)s(-1) was observed for the polydopamine-coated material-over 4.5 times greater than the uncoated nanocomposite and superior to those reported for similar carbon-supported metal catalysts. Simply integrating an inexpensive bioinspired polymer coating onto the Mn-graphene nanocomposite increased ORR performance significantly, with a peak potential shift of over +730 mV. This indicates that the material can reduce oxygen at a higher rate but with lower energy usage, revealing its excellent potential as an ORR electrocatalyst in fuel cells.

Progress in LPI Experiments at the NikeLaser

NASA Astrophysics Data System (ADS)

Weaver, J.; Kehne, D.; Obenschain, S.; Schmitt, A.; Serlin, V.; Oh, J.; Lehmberg, R.; Tsung, F.; McKenty, P.; Seely, J.

2014-10-01

The experimental program at the Nike laser facility at NRL is studying laser plasma instabilities (LPI) in the quarter critical region and cross-beam energy transport (CBET). The Nike krypton-fluorine (KrF) laser has unique characteristics that allow parametric studies of LPI. These features include short wavelength (248 nm), large bandwidth (~2-3 THz), beam smoothing by induced spatial incoherence (ISI), and full aperture focal spot zooming during the laser pulse. Nike also has a unique beam geometry that combines two widely separated beam arrays (145° in azimuth) with close beam-beam spacing (as low as 3.5°) within the main drive array. Particularly relevant for the CBET studies, recent campaigns have demonstrated the capability to alter the laser bandwidth by a factor of ~10 as well as shifts in the peak laser wavelength. An extensive LPI diagnostic suite is available for observation of stimulated Raman scattering, two-plasmon decay, stimulated Brillouin scattering, the parametric decay instability, and hard x-ray emission due to hot electrons. An overview of the observations of scattered laser light made during the previous studies of instabilities in the quarter critical region will be presented. Ongoing analysis of observed LPI emission from rotated targets will also be included. Plans for upcoming experiments related to quarter critical instabilities and CBET will be discussed. Work supported by DoE/NNSA.

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

Lebarbier Dagel, Vanessa M.; Li, J.; Taylor, Charles E.

This collaborative joint research project is in the area of advanced gasification and conversion, within the Chinese Academy of Sciences (CAS)-National Energy Technology Laboratory (NETL)-Pacific Northwest National Laboratory (PNNL) Memorandum of Understanding. The goal for this subtask is the development of advanced syngas conversion technologies. Two areas of investigation were evaluated: Sorption-Enhanced Synthetic Natural Gas Production from Syngas The conversion of synthetic gas (syngas) to synthetic natural gas (SNG) is typically catalyzed by nickel catalysts performed at moderate temperatures (275 to 325°C). The reaction is highly exothermic and substantial heat is liberated, which can lead to process thermal imbalance andmore » destruction of the catalyst. As a result, conversion per pass is typically limited, and substantial syngas recycle is employed. Commercial methanation catalysts and processes have been developed by Haldor Topsoe, and in some reports, they have indicated that there is a need and opportunity for thermally more robust methanation catalysts to allow for higher per-pass conversion in methanation units. SNG process requires the syngas feed with a higher H2/CO ratio than typically produced from gasification processes. Therefore, the water-gas shift reaction (WGS) will be required to tailor the H2/CO ratio. Integration with CO2 separation could potentially eliminate the need for a separate WGS unit, thereby integrating WGS, methanation, and CO2 capture into one single unit operation and, consequently, leading to improved process efficiency. The SNG process also has the benefit of producing a product stream with high CO2 concentrations, which makes CO2 separation more readily achievable. The use of either adsorbents or membranes that selectively separate the CO2 from the H2 and CO would shift the methanation reaction (by driving WGS for hydrogen production) and greatly improve the overall efficiency and economics of the process. The scope of this activity was to develop methods and enabling materials for syngas conversion to SNG with readily CO2 separation. Suitable methanation catalyst and CO2 sorbent materials were developed. Successful proof-of-concept for the combined reaction-sorption process was demonstrated, which culminated in a research publication. With successful demonstration, a decision was made to switch focus to an area of fuels research of more interest to all three research institutions (CAS-NETL-PNNL). Syngas-to-Hydrocarbon Fuels through Higher Alcohol Intermediates There are two types of processes in syngas conversion to fuels that are attracting R&D interest: 1) syngas conversion to mixed alcohols; and 2) syngas conversion to gasoline via the methanol-to-gasoline process developed by Exxon-Mobil in the 1970s. The focus of this task was to develop a one-step conversion technology by effectively incorporating both processes, which is expected to reduce the capital and operational cost associated with the conversion of coal-derived syngas to liquid fuels. It should be noted that this work did not further study the classic Fischer-Tropsch reaction pathway. Rather, we focused on the studies for unique catalyst pathways that involve the direct liquid fuel synthesis enabled by oxygenated intermediates. Recent advances made in the area of higher alcohol synthesis including the novel catalytic composite materials recently developed by CAS using base metal catalysts were used.« less

Polarity control at interfaces: Quantifying pseudo-solvent effects in nano-confined systems

DOE PAGES

Singappuli-Arachchige, Dilini; Manzano, J. Sebastian; Sherman, Lindy M.; ...

2016-08-02

Surface functionalization controls local environments and induces solvent-like effects at liquid–solid interfaces. We explored structure–property relationships between organic groups bound to pore surfaces of mesoporous silica nanoparticles and Stokes shifts of the adsorbed solvatochromic dye Prodan. Correlating shifts of the dye on the surfaces with its shifts in solvents resulted in a local polarity scale for functionalized pores. The scale was validated by studying the effects of pore polarity on quenching of Nile Red fluorescence and on the vibronic band structure of pyrene. Measurements were done in aqueous suspensions of porous particles, proving that the dielectric properties in the poresmore » are different from the bulk solvent. The precise control of pore polarity was used to enhance the catalytic activity of TEMPO in the aerobic oxidation of furfuryl alcohol in water. Furthermore, an inverse relationship was found between pore polarity and activity of TEMPO in the pores, demonstrating that controlling the local polarity around an active site allows modulating the activity of nanoconfined catalysts.« less

Shift and Day Work: A Comparison of Sickness Absence, Lateness, and other Absence Behaviour at an Oil Refinery from 1962 to 1965

PubMed Central

Taylor, P. J.

1967-01-01

Despite the increasing use of continuous process shift work in modern industry, few studies on the medical aspects of shift work can be found in recent literature of occupational health. Physiologists have shown that the ability of the body to adjust its circadian rhythms to alteration in hours of work or sleep can take up to a month. The usual type of shift work in industry involves weekly changes of hours, and thus on theoretical grounds at least this may not be the most suitable frequency for shift changes. Sickness absence of male refinery workers has been studied over a four-year period. The figures show that continuous three-cycle shift workers have consistently and significantly lower rates of sickness than day workers in similar occupations. The annual inception rate (spells) standardized for age was 108% for shift workers and 182% for day workers, and the average annual duration per man was 11 days for shift workers and 18 days for day workers, although the average length of spell was slightly longer among shift workers. As far as is known, such a difference has not been described before in detail. Age-related lateness and absenteeism have been measured and show similar wide differences between the two groups. Although both types of worker are largely self-selected, the difference is not due to medical selection or to an excess of any one type of disease in day workers. Over three-quarters of 150 shift workers interviewed stated that they preferred shift work hours and that sleeping difficulties were not common. It is suggested that the main reasons for the difference between shift and day workers' sickness absence lie in the degree of personal involvement in the work and in the social structure of the working group. PMID:6023084

From charity to caring: Nightingale's experience at Harley Street.

PubMed

Selanders, Louise C; Lake, Karen; Crane, Patrick

2010-12-01

Florence Nightingale has been the subject of numerous biographies and topical studies since she became a public figure during the Crimean War of 1854-1856. However, both the biographical and the topical literature have given little emphasis to the fourteen months of Nightingale's superintendency at The Establishment for Gentlewomen During Illness located on Harley Street, London. Thematic analysis of primary documents including Nightingale's Quarterly Reports to the Governors of her Nursing Home and the recently identified found Minutes of the Ladies' Committee of the Establishment of Gentlewomen During Illness were utilized to identify specific themes considered essential to Nightingale's professional and philosophical development. Harley Street proved to be the catalyst of opportunity that later launched her into the public view as a visionary through which she was to develop nursing as a profession and promote nursing as a legitimate route for women's education and employment.

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

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

PubMed

Han, Zhong-Kang; Gao, Yi

2016-02-01

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

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.

Electrochemical transformation of trichloroethylene in aqueous solution by electrode polarity reversal.

PubMed

Rajic, Ljiljana; Fallahpour, Noushin; Yuan, Songhu; Alshawabkeh, Akram N

2014-12-15

Electrode polarity reversal is evaluated for electrochemical transformation of trichloroethylene (TCE) in aqueous solution using flow-through reactors with mixed metal oxide electrodes and Pd catalyst. The study tests the hypothesis that optimizing electrode polarity reversal will generate H2O2 in Pd presence in the system. The effect of polarity reversal frequency, duration of the polarity reversal intervals, current intensity and TCE concentration on TCE removal rate and removal mechanism were evaluated. TCE removal efficiencies under 6 cycles h(-1) were similar in the presence of Pd catalyst (50.3%) and without Pd catalyst (49.8%), indicating that Pd has limited impact on TCE degradation under these conditions. The overall removal efficacies after 60 min treatment under polarity reversal frequencies of 6, 10, 15, 30 and 90 cycles h(-1) were 50.3%, 56.3%, 69.3%, 34.7% and 23.4%, respectively. Increasing the frequency of polarity reversal increases TCE removal as long as sufficient charge is produced during each cycle for the reaction at the electrode. Electrode polarity reversal shifts oxidation/reduction and reduction/oxidation sequences in the system. The optimized polarity reversal frequency (15 cycles h(-1) at 60 mA) enables two reaction zones formation where reduction/oxidation occurs at each electrode surface. Published by Elsevier Ltd.

Electrochemical transformation of trichloroethylene in aqueous solution by electrode polarity reversal

PubMed Central

Rajic, Ljiljana; Fallahpour, Noushin; Yuan, Songhu; Alshawabkeh, Akram N.

2014-01-01

Electrode polarity reversal is evaluated for electrochemical transformation of trichloroethylene (TCE) in aqueous solution using flow-through reactors with mixed metal oxide electrodes and Pd catalyst. The study tests the hypothesis that optimizing electrode polarity reversal will generate H2O2 in Pd presence in the system. The effect of polarity reversal frequency, duration of the polarity reversal intervals, current intensity and TCE concentration on TCE removal rate and removal mechanism were evaluated. TCE removal efficiencies under 6 cycles h−1 were similar in the presence of Pd catalyst (50.3%) and without Pd catalyst (49.8%), indicating that Pd has limited impact on TCE degradation under these conditions. The overall removal efficacies after 60 min treatment under polarity reversal frequencies of 6, 10, 15, 30 and 90 cycles h−1 were 50.3%, 56.3%, 69.3%, 34.7% and 23.4%, respectively. Increasing the frequency of polarity reversal increases TCE removal as long as sufficient charge is produced during each cycle for the reaction at the electrode. Electrode polarity reversal shifts oxidation/reduction and reduction/oxidation sequences in the system. The optimized polarity reversal frequency (15 cycles h−1 at 60 mA) enables two reaction zones formation where reduction/oxidation occurs at each electrode surface. PMID:25282093

Ni nanoparticles and the Kirkendall effect in dry reforming of methane

NASA Astrophysics Data System (ADS)

Pegios, N.; Bliznuk, V.; Theofanidis, S. A.; Galvita, V. V.; Marin, G. B.; Palkovits, R.; Simeonov, K.

2018-09-01

In this study we report a simple preparation technique for Ni/γ-Al2O3 catalysts for the dry reforming of methane (DRM) at 800 °C to produce CO and H2 (synthesis gas). Hard-templating with low and high surface area activated carbon was applied. The produced synthesis gas exhibited a low product ratio of H2:CO [0.04-0.12], due to reverse water-gas shift. After 75 h time on stream (TOS) minimal deactivation of the catalyst could be observed. A rather unusual activity evolution was found involving a sequence of minimum-maximum-plateau. A scheme was suggested, explaining the activity evolution based on the Ni-nanoparticle positioning from being bare or encapsulated by Al2O3. The Al2O3 shell cracks and undergoes restructuring during reaction making more active sites available for the reaction. Superior metal dispersion was achieved with average nickel nanoparticle size at 4.9 ± 1.3 nm. The sintering mechanism was also investigated. Surprisingly, hollow nickel nanoparticles were observed at 25 h TOS due to the nanoscale Kirkendall effect. This diffusion phenomenon between the core, Ni0, and the outer shell, NiO, (Ni2+) lead to pronounced structural and morphological changes of the catalyst.

Electromagnetic Characterization of Carbon Nanotube Films Subject to an Oxidative Treatment at Elevated Temperature (Preprint)

DTIC Science & Technology

2010-07-01

response to the tip causes a redistribution of charge on the tip in order to maintain the equipotential surface of the sphere, and also results in a shift...can be obtained. In some instances these treatments lead to uncapping of nanotubes. Geng et al. [25] have shown that the surfaces of SWNT bundles...20] discovered a new and catalyst-free method for the growth of CNTs: surface decomposition of silicon carbide (SiC). This thermal decomposition

Theoretical study on the mechanism of aqueous synthesis of formic acid catalyzed by [Ru3+]-EDTA complex.

PubMed

Chen, Zhe-Ning; Chan, Kwong-Yu; Pulleri, Jayasree K; Kong, Jing; Hu, Hao

2015-02-16

Because formic acid can be effectively decomposed by catalysis into very pure hydrogen gas, the synthesis of formic acid, especially using CO and H2O as an intermediate of the water gas shift reaction (WGSR), bears important application significance in industrial hydrogen gas production. Here we report a theoretical study on the mechanism of efficient preparation of formic acid using CO and H2O catalyzed by a water-soluble [Ru(3+)]-EDTA complex. To determine the feasibility of using the [Ru(3+)]-EDTA catalyst to produce CO-free hydrogen gas in WGSR, two probable reaction paths have been examined: one synthesizes formic acid, while the other converts the reactants directly into CO2 and H2, the final products of WGSR. Our calculation results provide a detailed mechanistic rationalization for the experimentally observed selective synthesis of HCOOH by the [Ru(3+)]-EDTA catalyst. The results support the applicability of using the [Ru(3+)]-EDTA catalyst to efficiently synthesize formic acid for hydrogen production. Careful analyses of the electronic structure and interactions of different reaction complexes suggest that the selectivity of the reaction processes is achieved through the proper charge/valence state of the metal center of the [Ru(3+)]-EDTA complex. With the catalytic roles of the ruthenium center and the EDTA ligand being carefully understood, the detailed mechanistic information obtained in this study will help to design more efficient catalysts for the preparation of formic acid and further to produce CO-free H2 at ambient temperature.

Pd/Cu-Oxide Nanoconjugate at Zeolite-Y Crystallite Crafting the Mesoporous Channels for Selective Oxidation of Benzyl-Alcohols.

PubMed

Sharma, Mukesh; Das, Biraj; Sharma, Mitu; Deka, Biplab K; Park, Young-Bin; Bhargava, Suresh K; Bania, Kusum K

2017-10-11

Solid-state grinding of palladium and copper salts allowed the growth of palladium/copper oxide interface at the zeolite-Y surface. The hybrid nanostructured material was used as reusable heterogeneous catalyst for selective oxidation of various benzyl alcohols. The large surface area provided by the zeolite-Y matrix highly influenced the catalytic activity, as well as the recyclability of the synthesized catalyst. Impregnation of PdO-CuO nanoparticles on zeolite crystallite leads to the generation of mesoporous channel that probably prevented the leaching of the metal-oxide nanoparticles and endorsed high mass transfer. Formation of mesoporous channel at the external surface of zeolite-Y was evident from transmission electron microscopy and surface area analysis. PdO-CuO nanoparticles were found to be within the range of 2-5 nm. The surface area of PdO-CuO-Y catalyst was found to be much lower than parent zeolite-Y. The decrease in surface area as well as the presence of hysteresis loop in the N 2 -adsoprtion isotherm further suggested successful encapsulation of PdO-CuO nanoparticles via the mesoporous channel formation. The high positive shifting in binding energy in both Pd and Cu was attributed to the influence of zeolite-Y framework on lattice contraction of metal oxides via confinement effect. PdO-CuO-Y catalyst was found to oxidize benzyl alcohol with 99% selectivity. On subjecting to microwave irradiation the same oxidation reaction was found to occur at ambient condition giving same conversion and selectivity.

High-indexed Pt 3Ni alloy tetrahexahedral nanoframes evolved through preferential CO etching

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

Wang, Chenyu; Zhang, Lihua; Yang, Hongzhou

2017-03-07

Here, chemically controlling crystal structures in nanoscale is challenging, yet provides an effective way to improve catalytic performances. Pt-based nanoframes are a new class of nanomaterials that have great potential as high-performance catalysts. To date, these nanoframes are formed through acid etching in aqueous solutions, which demands long reaction time and often yields ill-defined surface structures. Herein we demonstrate a robust and unprecedented protocol for facile development of high-performance nanoframe catalysts using size and crystallographic facet-controlled PtNi 4 tetrahexahedral nanocrystals prepared through a colloidal synthesis approach as precursors. This new protocol employs the Mond process to preferentially dealloy nickel componentmore » in the <100> direction through carbon monoxide etching of carbon-supported PtNi 4 tetrahexahedral nanocrystals at an elevated temperature. The resultant Pt 3Ni alloy tetrahexahedral nanoframes possess an open, stable, and high-indexed microstructure, containing a segregated Pt thin layer strained to the Pt–Ni alloy surfaces and featuring a down-shift d-band center as revealed by the density functional theory calculations. These nanoframes exhibit much improved catalytic performance, such as high stability under prolonged electrochemical potential cycles, promoting direct electro-oxidation of formic acid to carbon dioxide and enhancing oxygen reduction reaction activities. Because carbon monoxide can be generated from the carbon support through thermal annealing in air, a common process for pretreating supported catalysts, the developed approach can be easily adopted for preparing industrial scale catalysts that are made of Pt–Ni and other alloy nanoframes.« less

Impact of lubricant additives on the physicochemical properties and activity of three-way catalysts

DOE PAGES

Toops, Todd J.; Lance, Michael J.; Qu, Jun; ...

2016-04-04

As alternative lubricant anti-wear additives are sought to reduce friction and improve overall fuel economy, it is important that these additives are also compatible with current emissions control catalysts. In the present work, an oil-miscible phosphorous-containing ionic liquid (IL), trihexyltetradecylphosphonium bis(2-ethylhexyl) phosphate ([P 66614][DEHP]), is evaluated for its impact on three-way catalysts (TWC) and benchmarked against the industry standard zinc-dialkyl-dithio-phosphate (ZDDP). The TWCs are aged in different scenarios: neat gasoline (no-additive, or NA), gasoline+ZDDP, and gasoline+IL. The aged samples, along with the as received TWC, are characterized through various analytical techniques including catalyst reactivity evaluation in a bench-flow reactor. Themore » temperatures of 50% conversion (T50) for the ZDDP-aged TWCs increased by 30, 24, and 25 °C for NO, CO, and C3H6, respectively, compared to the no-additive case. Although the IL-aged TWC also increased in T50 for CO and C3H6, it was notably less than ZDDP, 7 and 9 °C, respectively. Additionally, the IL-aged samples had higher water-gas-shift reactivity and oxygen storage capacity than the ZDDP-aged TWC. Characterization of the aged samples indicated the predominant presence of CePO 4 in the ZDDP-aged TWC aged by ZDDP, while its formation was retarded in the case of IL where higher levels of AlPO 4 is observed. Furthermore, the results in this work indicate that the phosphonium-phosphate IL potentially has less adverse impact on TWC than ZDDP.« less

Impact of lubricant additives on the physicochemical properties and activity of three-way catalysts

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

Toops, Todd J.; Lance, Michael J.; Qu, Jun

As alternative lubricant anti-wear additives are sought to reduce friction and improve overall fuel economy, it is important that these additives are also compatible with current emissions control catalysts. In the present work, an oil-miscible phosphorous-containing ionic liquid (IL), trihexyltetradecylphosphonium bis(2-ethylhexyl) phosphate ([P 66614][DEHP]), is evaluated for its impact on three-way catalysts (TWC) and benchmarked against the industry standard zinc-dialkyl-dithio-phosphate (ZDDP). The TWCs are aged in different scenarios: neat gasoline (no-additive, or NA), gasoline+ZDDP, and gasoline+IL. The aged samples, along with the as received TWC, are characterized through various analytical techniques including catalyst reactivity evaluation in a bench-flow reactor. Themore » temperatures of 50% conversion (T50) for the ZDDP-aged TWCs increased by 30, 24, and 25 °C for NO, CO, and C3H6, respectively, compared to the no-additive case. Although the IL-aged TWC also increased in T50 for CO and C3H6, it was notably less than ZDDP, 7 and 9 °C, respectively. Additionally, the IL-aged samples had higher water-gas-shift reactivity and oxygen storage capacity than the ZDDP-aged TWC. Characterization of the aged samples indicated the predominant presence of CePO 4 in the ZDDP-aged TWC aged by ZDDP, while its formation was retarded in the case of IL where higher levels of AlPO 4 is observed. Furthermore, the results in this work indicate that the phosphonium-phosphate IL potentially has less adverse impact on TWC than ZDDP.« less

A Facile Molecular Precursor Route to Metal Phosphide Nanoparticles and Their Evaluation as Hydrodeoxygenation Catalysts

DOE PAGES

Habas, Susan E.; Baddour, Frederick G.; Ruddy, Daniel A.; ...

2015-11-05

Metal phosphides have been identified as a promising class of materials for the catalytic upgrading of bio-oils, which are renewable and potentially inexpensive sources for liquid fuels. Herein, we report the facile synthesis of a series of solid, phase-pure metal phosphide nanoparticles (NPs) (Ni 2P, Rh 2P, and Pd 3P) utilizing commercially available, air-stable metal–phosphine complexes in a one-pot reaction. This single-source molecular precursor route provides an alternative method to access metal phosphide NPs with controlled phases and without the formation of metal NP intermediates that can lead to hollow particles. The formation of the Ni 2P NPs was shownmore » to proceed through an amorphous Ni–P intermediate, leading to the desired NP morphology and metal-rich phase. This low-temperature, rapid route to well-defined metal NPs is expected to have broad applicability to a variety of readily available or easily synthesized metal–phosphine complexes with high decomposition temperatures. Hydrodeoxygenation of acetic acid, an abundant bio-oil component, was performed to investigate H 2 activation and deoxygenation pathways under conditions that are relevant to ex situ catalytic fast pyrolysis (high temperatures, low pressures, and near-stoichiometric H 2 concentrations). The catalytic performance of the silica-supported metal phosphide NPs was compared to the analogous incipient wetness (IW) metal and metal phosphide catalysts over the range 200–500 °C. Decarbonylation was the primary pathway for H 2 incorporation in the presence of all of the catalysts except NP-Pd 3P, which exhibited minimal productive activity, and IW-Ni, which evolved H 2. The highly controlled NP-Ni2P and NP-Rh2P catalysts, which were stable under these conditions, behaved comparably to the IW-metal phosphides, with a slight shift to higher product onset temperatures, likely due to the presence of surface ligands. Most importantly, the NP-Ni 2P catalyst exhibited H 2 activation and incorporation, in contrast to IW-Ni, indicating that the behavior of the metal phosphide is significantly different from that of the parent metal, and more closely resembles that of noble metal catalysts.« less

Advances of zeolite based membrane for hydrogen production via water gas shift reaction

NASA Astrophysics Data System (ADS)

Makertihartha, I. G. B. N.; Zunita, M.; Rizki, Z.; Dharmawijaya, P. T.

2017-07-01

Hydrogen is considered as a promising energy vector which can be obtained from various renewable sources. However, an efficient hydrogen production technology is still challenging. One technology to produce hydrogen with very high capacity with low cost is through water gas shift (WGS) reaction. Water gas shift reaction is an equilibrium reaction that produces hydrogen from syngas mixture by the introduction of steam. Conventional WGS reaction employs two or more reactors in series with inter-cooling to maximize conversion for a given volume of catalyst. Membrane reactor as new technology can cope several drawbacks of conventional reactor by removing reaction product and the reaction will favour towards product formation. Zeolite has properties namely high temperature, chemical resistant, and low price makes it suitable for membrane reactor applications. Moreover, it has been employed for years as hydrogen selective layer. This review paper is focusing on the development of membrane reactor for efficient water gas shift reaction to produce high purity hydrogen and carbon dioxide. Development of membrane reactor is discussed further related to its modification towards efficient reaction and separation from WGS reaction mixture. Moreover, zeolite framework suitable for WGS membrane reactor will be discussed more deeply.

Industry contributions to aggregate workplace injury and illness rate trends: 1992-2008.

PubMed

Ruser, John W

2014-10-01

Aggregate workplace injury and illness rates have generally declined over the past quarter century. Assessing which industries contributed to these declines is hampered by industry coding changes that broke time series data. Ratios were estimated to convert older incidence rate data to current industry codes and to create long industry time series from data of the BLS Survey of Occupational Injuries and Illnesses. These data were used to assess contributions to aggregate trends from within-industry incidence rate trends and across-industry hours shifts. Hours shifts toward safer industries do not explain aggregate incidence rate declines. Rather declines resulted from within-industry declines. The top 20 contributors out of 307 industries account for 40 percent of the decline and include both goods-producing and service-providing industries. These data help focus future research on industries responsible for rate declines and factors hypothesized as contributing to declines. © Published 2014 by Wiley Periodicals, Inc.

Ammonia reactions with the stored oxygen in a commercial lean NO x trap catalyst

DOE PAGES

Bartova, Sarka; Mracek, David; Koci, Petr; ...

2014-10-12

Ammonia is an important intermediate of the NO x reduction in a NO x storage and reduction catalyst (aka lean NO x trap). NH 3 formed under rich conditions in the reduced front part of the catalyst is transported by convection downstream to the unregenerated (still oxidized) zone of the catalyst, where it further reacts with the stored oxygen and NO x. In this paper, the kinetics and selectivity of NH 3 reactions with the stored oxygen are studied in detail with a commercial Ba-based NO x storage catalyst containing platinum group metals (PGM), Ba and Ce oxides. Furthermore, steady-statemore » NH 3 decomposition, NH 3 oxidation by O 2 and NO, and N 2O decomposition are examined in light-off experiments. Periodic lean/rich cycling is measured first with O 2 and NH 3, and then with NO x + O 2 and NH 3 to discriminate between the NH 3 reactions with the stored oxygen and the stored NO x. The reaction of NH 3 with the stored O 2 is highly selective towards N 2, however a certain amount of NO x and N 2O is also formed. The formed NO x by-product is efficiently adsorbed on the NO x storage sites such that the NO x is not detected at the reactor outlet except at high temperatures. The stored NO x reacts with NH 3 feed in the next rich phase, contributing to the N 2O formation. Water inhibits the reactions of NH 3 with the stored oxygen. On the contrary, the presence of CO 2 increases the NH 3 consumption. Furthermore, CO 2 is able to provide additional oxygen for NH 3 oxidation, forming –CO in analogy to the reverse water gas shift reaction.« less

Tracking Catalyst Redox States and Reaction Dynamics in Ni-Fe Oxyhydroxide Oxygen Evolution Reaction Electrocatalysts: The Role of Catalyst Support and Electrolyte pH.

PubMed

Görlin, Mikaela; Ferreira de Araújo, Jorge; Schmies, Henrike; Bernsmeier, Denis; Dresp, Sören; Gliech, Manuel; Jusys, Zenonas; Chernev, Petko; Kraehnert, Ralph; Dau, Holger; Strasser, Peter

2017-02-08

Ni-Fe oxyhydroxides are the most active known electrocatalysts for the oxygen evolution reaction (OER) in alkaline electrolytes and are therefore of great scientific and technological importance in the context of electrochemical energy conversion. Here we uncover, investigate, and discuss previously unaddressed effects of conductive supports and the electrolyte pH on the Ni-Fe(OOH) catalyst redox behavior and catalytic OER activity, combining in situ UV-vis spectro-electrochemistry, operando electrochemical mass spectrometry (DEMS), and in situ cryo X-ray absorption spectroscopy (XAS). Supports and pH > 13 strongly enhanced the precatalytic voltammetric charge of the Ni-Fe oxyhydroxide redox peak couple, shifted them more cathodically, and caused a 2-3-fold increase in the catalytic OER activity. Analysis of DEMS-based faradaic oxygen efficiency and electrochemical UV-vis traces consistently confirmed our voltammetric observations, evidencing both a more cathodic O 2 release and a more cathodic onset of Ni oxidation at higher pH. Using UV-vis, which can monitor the amount of oxidized Ni +3/+4 in situ, confirmed an earlier onset of the redox process at high electrolyte pH and further provided evidence of a smaller fraction of Ni +3/+4 in mixed Ni-Fe centers, confirming the unresolved paradox of a reduced metal redox activity with increasing Fe content. A nonmonotonic super-Nernstian pH dependence of the redox peaks with increasing Fe content-displaying Pourbaix slopes as steep as -120 mV/pH-suggested a two proton-one electron transfer. We explain and discuss the experimental pH effects using refined coupled (PCET) and decoupled proton transfer-electron transfer (PT/ET) schemes involving negatively charged oxygenate ligands generated at Fe centers. Together, we offer new insight into the catalytic reaction dynamics and associated catalyst redox chemistry of the most important class of alkaline OER catalysts.

Warm Cleanup of Coal-Derived Syngas: Multicontaminant Removal Process Demonstration

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

Spies, Kurt A.; Rainbolt, James E.; Li, Xiaohong S.

Warm cleanup of coal- or biomass-derived syngas requires sorbent and catalytic beds to protect downstream processes and catalysts from fouling. Sulfur is particularly harmful because even parts-per-million amounts are sufficient to poison downstream synthesis catalysts. Zinc oxide (ZnO) is a conventional sorbent for sulfur removal; however, its operational performance using real gasifier-derived syngas and in an integrated warm cleanup process is not well reported. In this paper, we report the optimal temperature for bulk desulfurization to be 450oC, while removal of sulfur to parts-per-billion levels requires a lower temperature of approximately 350oC. Under these conditions, we found that sulfur inmore » the form of both hydrogen sulfide and carbonyl sulfide could be absorbed equally well using ZnO. For long-term operation, sorbent regeneration is desirable to minimize process costs. Over the course of five sulfidation and regeneration cycles, a ZnO bed lost about a third of its initial sulfur capacity, however sorbent capacity stabilized. Here, we also demonstrate, at the bench-scale, a process and materials used for warm cleanup of coal-derived syngas using five operations: 1) Na2CO3 for HCl removal, 2) regenerable ZnO beds for bulk sulfur removal, 3) a second ZnO bed for trace sulfur removal, 4) a Ni-Cu/C sorbent for multi-contaminant inorganic removal, and 5) a Ir-Ni/MgAl2O4 catalyst employed for ammonia decomposition and tar and light hydrocarbon steam reforming. Syngas cleanup was demonstrated through successful long-term performance of a poison-sensitive, Cu-based, water-gas-shift catalyst placed downstream of the cleanup process train. The tar reformer is an important and necessary operation with this particular gasification system; its inclusion was the difference between deactivating the water-gas catalyst with carbon deposition and successful 100-hour testing using 1 LPM of coal-derived syngas.« less

Lunar influence on prey availability, diet shifts and niche overlap between Engraulidae larvae in tropical mangrove creeks.

PubMed

Lima, A R A; Barletta, M

2016-10-01

The influence of the lunar cycle on prey availability, diet shifts and overlap between larval Anchovia clupeoides and Cetengraulis edentulus was evaluated in mangrove creeks of the Goiana Estuary. Copepod eggs were highly abundant in the first and last quarter, at the full moon and zoea of Ucides cordatus (Ocypodidae) in the new moon. The Engraulidae larvae fed on microcrustaceans, algae and early planktonic stages of benthic organisms. The relative importance of prey varied according to prey availability in all moon phases. Larval diets were more even in the full and new moons, when the relative importance of calanoid copepods and zoeae of U. cordatus as food items increased (index of relative importance, >80% I RI ). Mangrove creeks were very important feeding grounds for engraulid larvae during spring tides. Larval diets were more diverse in the first and last-quarter moon and included protozoeae of Caridean shrimp, larvae of Anomalocardia brasiliana (Veneridae), Isopoda, Gastropoda, ephippium of Daphnia sp. and nauplii of Cirripedia, Harpacticoidia and cyclopoid Copepoda. The last five items were not found in the creeks, suggesting feeding in the main channel. During neap tides, mangrove creeks were probably also used as refugia. These larvae are opportunistic and feed on highly available prey and both species feed on the same items, leading to high dietary overlap in all moon phases. The lunar cycle, which is related to the spring-neap tidal cycle, was the major driver of quantitative and qualitative changes in feeding of engraulid larvae on a short time scale. © 2016 The Fisheries Society of the British Isles.

Low severity coal conversion by ionic hydrogenation: Quarterly report, October--December 1988

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

Maioriello, J.; Larsen, J.W.

1988-12-31

A newly developed reaction system consisting of H/sub 2/O:BF/sub 3//H/sub 2//(CH/sub 3/CN)/sub 2/PtCl/sub 2/ was applied to the ionic hydrogenation of aromatic and functionalized aromatic compounds. Hydrogenations were carried out in this aqueous system at 50/degree/C and 500 psi H/sub 2/. Aryl ethers were hydrogenated and cleaved, yielding deoxygenated, fully saturated compounds as the major products. Reactions of nitrogen-containing aromatic compounds resulted in partial saturation of aromatic rings without cleavage of the C-N bonds. Aromatic and PNA compounds can be fully or partially hydrogenated depending on their structures. Aromatic thiols, sulfides and thiophenes poison the catalyst; the oxidized sulfur formsmore » (sulfonic acids, sulfones) were not reduced and did not poison the catalyst. It was found that certain aromatic compounds were easier to hydrogenate than others. Ionic hydrogenation of Wyodak cola using a H/sub 2/O:BF/sub 3//H/sub 2//(MeCN)/sub 2/PtCl/sub 2/ resulted in no significant increase in THF extractability (5.8--9.6% THF-extractables, wt) over that of the parent coal (4.6--6.7% THF-extractables, wt). Ionic hydrogenation of a demineralized Wyodak coal (1 M aq. citric acid, reflux 1 day) resulted in a slight increase in THF extractability (10.4%) over the untreated parent coal (5.6--5.8%). 4 refs., 1 fig., 1 tab.« less

Advanced direct coal liquefaction concepts. Quarterly report, April 1, 1993--June 30, 1993

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

Berger, D.J.; Parker, R.J.; Simpson, P.L.

Construction and commissioning of the bench unit for operation of the first stage of the process was completed. Solubilization of Black Thunder coal using carbon monoxide and steam was successfully demonstrated in the counterflow reactor system. The results were comparable with those obtained in the autoclave with the exception that coal solubilization at the same nominal residence times was slightly lower. The bench unit has now been modified for two stage operation. The Wilsonville process derived solvent for Black Thunder coal (V-1074) was found to be essentially as stable as the previous solvent used in the autoclave runs (V-178 +more » 320) at reactor conditions. This solvent (V-1074) is, therefore, being used in the bench unit tests. Carbon monoxide may be replaced by synthesis gas for the coal solubilization step in the process. However, in autoclave tests, coal conversion was found to be dependent on the amount of carbon monoxide present in the synthesis gas. Coal conversions ranged from 88% for pure carbon monoxide to 67% for a 25:75 carbon monoxide/hydrogen mixture at equivalent conditions. Two stage liquefaction tests were completed in the autoclave using a disposable catalyst (FeS) and hydrogen in the second stage. Increased coal conversion, higher gas and oil and lower asphaltene and preasphaltene yields were observed as expected. However, no hydrogen consumption was observed in the second stage. Other conditions, in particular, alternate catalyst systems will be explored.« less

Water–gas shift reaction over gold nanoparticles dispersed on nanostructured CeO x–TiO 2(110) surfaces: Effects of high ceria coverage

DOE PAGES

Grinter, D. C.; Park, J. B.; Agnoli, S.; ...

2016-08-01

We used scanning tunnelling microscopy to study the morphology of an overlayer of ceria in contact with a TiO 2(110) substrate. Two types of domains were observed after ceria deposition. An ordered ceria film covered half of the surface and high-resolution imaging suggested a near-c(6 × 2) relationship to the underlying TiO 2(110)-(1 × 1). For the other half of the surface, it comprised CeO x nanoparticles and reconstructed TiOx supported on TiO 2(110)-(1 × 1). Exposure to a small amount of gold resulted in the formation of isolated gold atoms and small clusters on the ordered ceria film andmore » TiO 2(110)-(1 × 1) areas, which exhibited significant sintering at 500 K and showed strong interaction between the sintered gold clusters and the domain boundaries of the ceria film. The Au/CeO x/TiO 2(110) model system proved to be a good catalyst for the water–gas shift (WGS) exhibiting much higher turnover frequencies (TOFs) than Cu(111) and Pt(111) benchmarks, or the individual Au/TiO 2(110) and Au/CeO 2(111) systems. Finally, for Au/CeO x/TiO 2(110) catalysts, there was a decrease in catalytic activity with increasing ceria coverage that correlates with a reduction in the concentration of Ce 3 + formed during WGS reaction conditions.« less

Water–gas shift reaction over gold nanoparticles dispersed on nanostructured CeO x–TiO 2(110) surfaces: Effects of high ceria coverage

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

Grinter, D. C.; Park, J. B.; Agnoli, S.

We used scanning tunnelling microscopy to study the morphology of an overlayer of ceria in contact with a TiO 2(110) substrate. Two types of domains were observed after ceria deposition. An ordered ceria film covered half of the surface and high-resolution imaging suggested a near-c(6 × 2) relationship to the underlying TiO 2(110)-(1 × 1). For the other half of the surface, it comprised CeO x nanoparticles and reconstructed TiOx supported on TiO 2(110)-(1 × 1). Exposure to a small amount of gold resulted in the formation of isolated gold atoms and small clusters on the ordered ceria film andmore » TiO 2(110)-(1 × 1) areas, which exhibited significant sintering at 500 K and showed strong interaction between the sintered gold clusters and the domain boundaries of the ceria film. The Au/CeO x/TiO 2(110) model system proved to be a good catalyst for the water–gas shift (WGS) exhibiting much higher turnover frequencies (TOFs) than Cu(111) and Pt(111) benchmarks, or the individual Au/TiO 2(110) and Au/CeO 2(111) systems. Finally, for Au/CeO x/TiO 2(110) catalysts, there was a decrease in catalytic activity with increasing ceria coverage that correlates with a reduction in the concentration of Ce 3 + formed during WGS reaction conditions.« less

Vascular Surgery in World War II: The Shift to Repairing Arteries.

PubMed

Barr, Justin; Cherry, Kenneth J; Rich, Norman M

2016-03-01

Vascular surgery in World War II has long been defined by DeBakey and Simeone's classic 1946 article describing arterial repair as exceedingly rare. They argued ligation was and should be the standard surgical response to arterial trauma in war. We returned to and analyzed the original records of World War II military medical units housed in the National Archives and other repositories in addition to consulting published accounts to determine the American practice of vascular surgery in World War II. This research demonstrates a clear shift from ligation to arterial repair occurring among American military surgeons in the last 6 months of the war in the European Theater of Operations. These conclusions not only highlight the role of war as a catalyst for surgical change but also point to the dangers of inaccurate history in stymieing such advances.

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

Ji Shidong; Murakami, Setsuaki; Kamitakahara, Masanobu

The titania/hydroxyapatite composite granular photo-catalyst with novel microstructure was fabricated by the process based on the liquid immiscibility effect and followed by precalcination and hydrothermal treatment from commercially available powders of {alpha}-Tri-calcium phosphate and TiO{sub 2}. XRD, SEM, BET, optical microscopy and UV-vis spectrophotometer were applied to characterize the prepared photo-catalyst. Microstructure analysis indicated that the granule was weaved by rod-shaped hydroxyapatite crystals whose surface was covered by nano-sized TiO{sub 2}. In the composite granules, the active surface of anatase was retained effectively. With the hybridization of TiO{sub 2} and HAp, a 16-nm blue-shift of absorption edge could be observedmore » and the crystallinity of anatase could be enhanced by precalcination. The granules with the rod-shaped hydroxyapatite crystals performing as scaffold work as three-dimensional high porous, size-controllable small reactor. The phase and microstructure transformation of the granule before and after hydrothermal treatment was investigated and its decomposition ability was evaluated by using Methylene blue as a target pollutant compound.« less

Life and death of a single catalytic cracking particle

PubMed Central

Meirer, Florian; Kalirai, Sam; Morris, Darius; Soparawalla, Santosh; Liu, Yijin; Mesu, Gerbrand; Andrews, Joy C.; Weckhuysen, Bert M.

2015-01-01

Fluid catalytic cracking (FCC) particles account for 40 to 45% of worldwide gasoline production. The hierarchical complex particle pore structure allows access of long-chain feedstock molecules into active catalyst domains where they are cracked into smaller, more valuable hydrocarbon products (for example, gasoline). In this process, metal deposition and intrusion is a major cause for irreversible catalyst deactivation and shifts in product distribution. We used x-ray nanotomography of industrial FCC particles at differing degrees of deactivation to quantify changes in single-particle macroporosity and pore connectivity, correlated to iron and nickel deposition. Our study reveals that these metals are incorporated almost exclusively in near-surface regions, severely limiting macropore accessibility as metal concentrations increase. Because macropore channels are “highways” of the pore network, blocking them prevents feedstock molecules from reaching the catalytically active domains. Consequently, metal deposition reduces conversion with time on stream because the internal pore volume, although itself unobstructed, becomes largely inaccessible. PMID:26601160

Single Platinum Atoms Electrocatalysts: Oxygen Reduction and Hydrogen Oxidation Reactions

DOE PAGES

Vukmirovic, Miomir B.; Teeluck, Krishani M.; Liu, Ping; ...

2017-08-08

We prepared atomically dispersed catalyst consisting of Pt atoms arranged in a c(2 × 2) array on RuO2(110) substrate. A large interatomic distance of Pt atoms in a c(2 × 2) phase precludes the reactants to interact with more than one Pt atoms. A strong bond of Pt atoms with RuO2 prevents agglomeration of Pt atoms to form 2D-islands or 3D-clusters. The activities of single Pt atom catalyst for the oxygen reduction and hydrogen oxidation reactions were determined and compared with those of bulk Pt. It has lower catalytic activity for the oxygen reduction reaction and similar activity for hydrogenmore » oxidation reaction compared to Pt(111). This was explained by a large calculated up-shift of the dband center of Pt atoms and larger Pt-Pt interatomic distance than that of Pt(111). Our information is of considerable interest for further development of electrocatalysis.« less

ATOM-ECONOMICAL PATHWAYS TO METHANOL FUEL CELL FROM BIOMASS

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

MAHAJAN,D.; WEGRZYN,J.E.

1999-03-01

An economical production of alcohol fuels from biomass, a feedstock low in carbon and high in water content, is of interest. At Brookhaven National Laboratory (BNL), a Liquid Phase Low Temperature (LPLT) concept is under development to improve the economics by maximizing the conversion of energy carrier atoms (C,H) into energy liquids (fuel). So far, the LPLT concept has been successfully applied to obtain highly efficient methanol synthesis. This synthesis was achieved with specifically designed soluble catalysts, at temperatures < 150 C. A subsequent study at BNL yielded a water-gas-shift (WGS) catalyst for the production of hydrogen from a feedstockmore » of carbon monoxide and H{sub 2}O at temperatures < 120 C. With these LPLT technologies as a background, this paper extends the discussion of the LPLT concept to include methanol decomposition into 3 moles of H{sub 2} per mole of methanol. The implication of these technologies for the atom-economical pathways to methanol fuel cell from biomass is discussed.« less

Performance of a natural gas fuel processor for residential PEFC system using a novel CO preferential oxidation catalyst

NASA Astrophysics Data System (ADS)

Echigo, Mitsuaki; Shinke, Norihisa; Takami, Susumu; Tabata, Takeshi

Natural gas fuel processors have been developed for 500 W and 1 kW class residential polymer electrolyte fuel cell (PEFC) systems. These fuel processors contain all the elements—desulfurizers, steam reformers, CO shift converters, CO preferential oxidation (PROX) reactors, steam generators, burners and heat exchangers—in one package. For the PROX reactor, a single-stage PROX process using a novel PROX catalyst was adopted. In the 1 kW class fuel processor, thermal efficiency of 83% at HHV was achieved at nominal output assuming a H 2 utilization rate in the cell stack of 76%. CO concentration below 1 ppm in the product gas was achieved even under the condition of [O 2]/[CO]=1.5 at the PROX reactor. The long-term durability of the fuel processor was demonstrated with almost no deterioration in thermal efficiency and CO concentration for 10,000 h, 1000 times start and stop cycles, 25,000 cycles of load change.

[The causality of lunar changes on cardiovascular mortality].

PubMed

Sitar, J

1990-11-09

The author confirmed, based on different ways of processing of 1437 sudden cardiovascular deaths, that the frequency of these deaths changes in the course of the synodic moon with two maxima during the lunar quarters. Processing by the method of transfer of epochs made it possible to shift steadily the mortality curves according to the phase of solar activity. This made the author assume that the cause of the phenomenon of two-phasic change of mortality during lunation cannot be only gravitation (sudden tides) and that in addition the interfering influence of solar corpuscular radiation is involved. It is known that this radiation causes geomagnetic disorders. Consistent with the above view it was proved that in the course of lunation the greatest number of geomagnetic disorders occur at a time close to the lunar quarters. Then, as the author proved--aurora polaris is more frequent. The increased cardiovascular mortality is thus associated with an increased geomagnetic activity. The relationship is certainly not direct. The author indicates further trends of research to disclose the immediate causes which exert an unfavourable effect on our cardiovascular system.

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

Yang, Chan-Shan; Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720; Tang, Tsung-Ta

Indium Tin Oxide (ITO) nanowhiskers (NWhs) obliquely evaporated by electron-beam glancing-angle deposition can serve simultaneously as transparent electrodes and alignment layer for liquid crystal (LC) devices in the terahertz (THz) frequency range. To demonstrate, we constructed a THz LC phase shifter with ITO NWhs. Phase shift exceeding π/2 at 1.0 THz was achieved in a ∼517 μm-thick cell. The phase shifter exhibits high transmittance (∼78%). The driving voltage required for quarter-wave operation is as low as 5.66 V (rms), compatible with complementary metal-oxide-semiconductor (CMOS) and thin-film transistor (TFT) technologies.

Comparison of U.S. net import reliance for nonfuel mineral commodities—A 60-year retrospective (1954–1984–2014)

USGS Publications Warehouse

Fortier, Steven M.; DeYoung,, John H.; Sangine, Elizabeth S.; Schnebele, Emily K.

2015-12-14

The USGS–NMIC collects, analyzes, and disseminates information on a monthly, quarterly, or annual basis for more than 90 nonfuel mineral commodities from more than 180 countries. These data indicate that from 1954 through 2014 there was (1) a clear increase in the number and type of nonfuel mineral commodities for which the United States was net import reliant, (2) an increase in the percentage of import reliance for individual nonfuel mineral commodities, and (3) a shift in the geographic distribution of the source countries.

Inexpensive Audio Activities: Earbud-based Sound Experiments

NASA Astrophysics Data System (ADS)

Allen, Joshua; Boucher, Alex; Meggison, Dean; Hruby, Kate; Vesenka, James

2016-11-01

Inexpensive alternatives to a number of classic introductory physics sound laboratories are presented including interference phenomena, resonance conditions, and frequency shifts. These can be created using earbuds, economical supplies such as Giant Pixie Stix® wrappers, and free software available for PCs and mobile devices. We describe two interference laboratories (beat frequency and two-speaker interference) and two resonance laboratories (quarter- and half-wavelength). Lastly, a Doppler laboratory using rotating earbuds is explained. The audio signal captured by all experiments is analyzed on free spectral analysis software and many of the experiments incorporate the unifying theme of measuring the speed of sound in air.

Formation of C-C and C-O bonds and oxygen removal in reactions of alkanediols, alkanols, and alkanals on copper catalysts.

PubMed

Sad, María E; Neurock, Matthew; Iglesia, Enrique

2011-12-21

This study reports evidence for catalytic deoxygenation of alkanols, alkanals, and alkanediols on dispersed Cu clusters with minimal use of external H(2) and with the concurrent formation of new C-C and C-O bonds. These catalysts selectively remove O-atoms from these oxygenates as CO or CO(2) through decarbonylation or decarboxylation routes, respectively, that use C-atoms present within reactants or as H(2)O using H(2) added or formed in situ from CO/H(2)O mixtures via water-gas shift. Cu catalysts fully convert 1,3-propanediol to equilibrated propanol-propanal intermediates that subsequently form larger oxygenates via aldol-type condensation and esterification routes without detectable involvement of the oxide supports. Propanal-propanol-H(2) equilibration is mediated by their chemisorption and interconversion at surfaces via C-H and O-H activation and propoxide intermediates. The kinetic effects of H(2), propanal, and propanol pressures on turnover rates, taken together with measured selectivities and the established chemical events for base-catalyzed condensation and esterification reactions, indicate that both reactions involve kinetically relevant bimolecular steps in which propoxide species, acting as the base, abstract the α-hydrogen in adsorbed propanal (condensation) or attack the electrophilic C-atom at its carbonyl group (esterification). These weakly held basic alkoxides render Cu surfaces able to mediate C-C and C-O formation reactions typically catalyzed by basic sites inherent in the catalyst, instead of provided by coadsorbed organic moieties. Turnover rates for condensation and esterification reactions decrease with increasing Cu dispersion, because low-coordination corner and edge atoms prevalent on small clusters stabilize adsorbed intermediates and increase the activation barriers for the bimolecular kinetically relevant steps required for both reactions. © 2011 American Chemical Society

Building on transformative learning and response shift theory to investigate health-related quality of life changes over time in individuals with chronic health conditions and disability.

PubMed

Barclay-Goddard, Ruth; King, Judy; Dubouloz, Claire-Jehanne; Schwartz, Carolyn E

2012-02-01

A major goal of treatment for people living with chronic illness or disability is self-management leading to optimized health-related quality of life. This change process has been described in the adult education literature as transformative learning, while in health-related quality of life research, response shift has emerged as a key concept. Response shift and transformative learning literature were reviewed, and the theoretical frameworks of the 2 concepts were compared and contrasted. Response shift is described as a change in internal standards, values, or definition of a construct (eg, health-related quality of life) over time, commonly seen in individuals with chronic illness. In the context of chronic illness, transformative learning is described as a complex process of personal change including beliefs, feelings, knowledge, and values. Transformative learning is often triggered by the diagnosis of a chronic illness. This results in a critical reflection of taken-for-granted assumptions and leads to new ways of thinking, influencing personal changes in daily living. Comparing the models of response shift and transformative learning in chronic illness, the catalyst in response shift appears comparable with the trigger in transformational learning; mechanisms to process of changing; and perceived quality of life to outcomes. Both transformative learning and response shift have much to offer health care providers in understanding the learning process for the person living with chronic illness or disability to optimize their quality of life. Suggestions for future research in response shift and transformative learning in individuals with chronic health conditions and disability are proposed. Copyright © 2012 American Congress of Rehabilitation Medicine. Published by Elsevier Inc. All rights reserved.

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.

Photophysical studies of chromium sensitizers designed for excited state hole transfer to semiconductors and sequential hole/electron transfers from photoexcited cadmium sulfide nanorods to mononuclear ruthenium water-oxidation catalysts

NASA Astrophysics Data System (ADS)

Tseng, Huan-Wei

This dissertation describes three research projects related to solar cells and solar water splitting with a goal of utilizing solar energy, a renewable energy source. The first project is focused on photophysical studies of four newly-synthesized Cr(III) tris-bipyridyl complexes featuring the 4-dmcbpy (dimethyl 2,2'-bipyridine-4,4'-dicarboxylate) ligand. Static and time-resolved emission results suggest that the complexes store ˜1.7 eV of energy for multiple microseconds. Using cyclic voltammetry, it is found that the inclusion of 4-dmcbpy shifts the E1/2 of CrIII/II by +0.2 V from the homoleptic parent complexes without 4-dmcbpy. All four complexes have excited state potentials of CrIII*/II between +1.8 and +2.0 V vs. NHE, placing them among the most powerful photooxidants reported and making them candidates for hole-injection sensitizers. The second project continues with Cr(III) complexes, but using iminopyridine Schiff base ligands. Two complexes feature hexadentate ligands and the other two are their tris-bidentate analogues. One of each pair contains methyl ester groups for attachment to semiconductors. Cyclic voltammograms show that the hexadentate and tris-bidentate analogues have almost identical reduction potentials, but the addition of ester substituents shifts the reduction potentials by +0.2 V. The absorption spectra of the hexadentate complexes show improved absorption of visible light compared to the tris-bidentate analogues. For freshly prepared sample solutions in CH3CN, time-resolved emission and transient absorption measurements for the Cr(III) tris-bidentate ester complex show a doublet excited state with a 17-19 microsecond lifetime at room temperature, while no emission or transient absorption signals from the doublet states are observed for the hexadentate analogue under the same conditions. The dramatic difference is due to the presence of a nonligated bridgehead nitrogen atom. The third project features charge transfer interactions between a photoexcited cadmium sulfide nanorod and [Ru(diethyl 2,2'-bipyridine-4,4'-dicarboxylate)(2,2':6',2"-terpyridine)Cl] +, a mononuclear water-oxidation catalyst. Upon photoexcitation, hole transfer from the cadmium sulfide nanorod oxidizes the catalyst (Ru 2+ → Ru3+) on a 100 ps to 1 ns timescale. This is followed by electron transfer (10-100 ns) from the nanorod to reduce the Ru3+ center. The relatively slow electron transfer dynamics may provide opportunities for the accumulation of multiple holes at the catalyst, which is required for water oxidation.

The influence of iridium chemical oxidation state on the performance and durability of oxygen evolution catalysts in PEM electrolysis

NASA Astrophysics Data System (ADS)

Siracusano, S.; Baglio, V.; Grigoriev, S. A.; Merlo, L.; Fateev, V. N.; Aricò, A. S.

2017-10-01

Nanosized Ir-black (3 nm) and Ir-oxide (5 nm) oxygen evolution electrocatalysts showing high performance in polymer electrolyte membrane (PEM) water electrolysis based on Aquivion® short-side chain ionomer membrane are investigated to understand the role of the Ir oxidation state on the electrocatalytic activity and stability. Despite the smaller mean crystallite size, the Ir-black electrocatalyst shows significantly lower initial performance than the Ir-oxide. During operation at high current density, the Ir-black shows a decrease of cell potential with time whereas the Ir-oxide catalyst shows increasing cell potential resulting in a degradation rate of about 10 μV/h, approaching 1000 h. The unusual behaviour of the Ir-black results from the oxidation of metallic Ir to IrOx. The Ir-oxide catalyst shows instead a hydrated structure on the surface and a negative shift of about 0.5 eV for the Ir 4f binding energy after 1000 h electrolysis operation. This corresponds to the formation of a sub-stoichiometric Ir-oxide on the surface. These results indicate that a hydrated IrO2 with high oxidation state on the surface is favourable in decreasing the oxygen evolution overpotential. Modifications of the Ir chemical oxidation state during operation can affect significantly the catalytic activity and durability of the electrolysis system.

Evolving Maturation of the Series-Bosch System

NASA Technical Reports Server (NTRS)

Stanley, Christine; Abney, Morgan B.; Barnett, Bill

2017-01-01

Human exploration missions to Mars and other destinations beyond low Earth orbit require highly robust, reliable, and maintainable life support systems that maximize recycling of water and oxygen. In order to meet this requirement, NASA has continued the development of a Series-Bosch System, a two stage reactor process that reduces carbon dioxide (CO2) with hydrogen (H2) to produce water and solid carbon. Theoretically, the Bosch process can recover 100% of the oxygen (O2) from CO2 in the form of water, making it an attractive option for long duration missions. The Series Bosch system includes a reverse water gas shift (RWGS) reactor, a carbon formation reactor (CFR), an H2 extraction membrane, and a CO2 extraction membrane. In 2016, the results of integrated testing of the Series Bosch system showed great promise and resulted in design modifications to the CFR to further improve performance. This year, integrated testing was conducted with the modified reactor to evaluate its performance and compare it with the performance of the previous configuration. Additionally, a CFR with the capability to load new catalyst and remove spent catalyst in-situ was built. Flow demonstrations were performed to evaluate both the catalyst loading and removal process and the hardware performance. The results of the integrated testing with the modified CFR as well as the flow demonstrations are discussed in this paper.

Energy level shifts at the silica/Ru(0001) heterojunction driven by surface and interface dipoles

DOE PAGES

Wang, Mengen; Zhong, Jian -Qiang; Kestell, John; ...

2016-09-12

Charge redistribution at heterogeneous interfaces is a fundamental aspect of surface chemistry. Manipulating the amount of charges and the magnitude of dipole moments at the interface in a controlled way has attracted tremendous attention for its potential to modify the activity of heterogeneous catalysts in catalyst design. Two-dimensional ultrathin silica films with well-defined atomic structures have been recently synthesized and proposed as model systems for heterogeneous catalysts studies. R. Wlodarczyk et al. (Phys. Rev. B, 85, 085403 (2012)) have demonstrated that the electronic structure of silica/Ru(0001) can be reversibly tuned by changing the amount of interfacial chemisorbed oxygen. Here wemore » carried out systematic investigations to understand the underlying mechanism through which the electronic structure at the silica/Ru(0001) interface can be tuned. As corroborated by both in situ X-ray photoelectron spectroscopy and density functional theory calculations, the observed interface energy level alignments strongly depend on the surface and interfacial charge transfer induced dipoles at the silica/Ru(0001) heterojunction. These observations may help to understand variations in catalytic performance of the model system from the viewpoint of the electronic properties at the confined space between the silica bilayer and the Ru(0001) surface. As a result, the same behavior is observed for the aluminosilicate bilayer, which has been previously proposed as a model system for zeolites.« less

Visible and Near-Infrared Photothermal Catalyzed Hydrogenation of Gaseous CO2 over Nanostructured Pd@Nb2O5.

PubMed

Jia, Jia; O'Brien, Paul G; He, Le; Qiao, Qiao; Fei, Teng; Reyes, Laura M; Burrow, Timothy E; Dong, Yuchan; Liao, Kristine; Varela, Maria; Pennycook, Stephen J; Hmadeh, Mohamad; Helmy, Amr S; Kherani, Nazir P; Perovic, Doug D; Ozin, Geoffrey A

2016-10-01

The reverse water gas shift (RWGS) reaction driven by Nb 2 O 5 nanorod-supported Pd nanocrystals without external heating using visible and near infrared (NIR) light is demonstrated. By measuring the dependence of the RWGS reaction rates on the intensity and spectral power distribution of filtered light incident onto the nanostructured Pd@Nb 2 O 5 catalyst, it is determined that the RWGS reaction is activated photothermally. That is the RWGS reaction is initiated by heat generated from thermalization of charge carriers in the Pd nanocrystals that are excited by interband and intraband absorption of visible and NIR light. Taking advantage of this photothermal effect, a visible and NIR responsive Pd@Nb 2 O 5 hybrid catalyst that efficiently hydrogenates CO 2 to CO at an impressive rate as high as 1.8 mmol gcat -1 h -1 is developed. The mechanism of this photothermal reaction involves H 2 dissociation on Pd nanocrystals and subsequent spillover of H to the Nb 2 O 5 nanorods whereupon adsorbed CO 2 is hydrogenated to CO. This work represents a significant enhancement in our understanding of the underlying mechanism of photothermally driven CO 2 reduction and will help guide the way toward the development of highly efficient catalysts that exploit the full solar spectrum to convert gas-phase CO 2 to valuable chemicals and fuels.

The TQM Coordinator as Change Agent in Implementing Total Quality Management

DTIC Science & Technology

1989-06-01

Quality Management involves a major change, a paradigm shift, in management philosophy. Implementing TQM requires the use of a change agent to act as a catalyst to change the organization. Interviews with TQM coordinators, and a survey of 143 organizations were done to examine the role of the TQM coordinator. Research identified criteria for selection, and location in the organizational structure. Use of an external consultant in a tem concept is examined. Resistance to change and overcoming that resistance are explored. Ways to measure success are discussed. Keywords:

Bifunctional Catalysts for CO2 Reduction

DTIC Science & Technology

2014-09-30

hexane soluble material was crystallized at –35 ºC permitting characterization by X-ray diffraction to identify [(tbsL) Co3 (µ 3- N)]NBu4 as the product...of the trinuclear core and make atom and group-transfer processes even more facile. To probe this we investigated the reactivity of (tbsL) Co3 (py...Reaction of (tbsL) Co3 (py) with with Bu4N[N3] yields the azide adduct Bu4N[( tbsL) Co3 (µ 3-N3)] which features a C3-symmetric, paramagnetically shifted

Method for low temperature catalytic production of hydrogen

DOEpatents

Mahajan, Devinder

2003-07-22

The invention provides a process for the catalytic production of a hydrogen feed by exposing a hydrogen feed to a catalyst which promotes a base-catalyzed water-gas-shift reaction in a liquid phase. The hydrogen feed can be provided by any process known in the art of making hydrogen gas. It is preferably provided by a process that can produce a hydrogen feed for use in proton exchange membrane fuel cells. The step of exposing the hydrogen feed takes place preferably from about 80.degree. C. to about 150.degree. C.

Development and test fuel cell powered on-site integrated total energy systems. Phase 3: Full-scale power plant development

NASA Technical Reports Server (NTRS)

Kaufman, A.

1982-01-01

The on-site system application analysis is summarized. Preparations were completed for the first test of a full-sized single cell. Emphasis of the methanol fuel processor development program shifted toward the use of commercial shell-and-tube heat exchangers. An improved method for predicting the carbon-monoxide tolerance of anode catalysts is described. Other stack support areas reported include improved ABA bipolar plate bonding technology, improved electrical measurement techniques for specification-testing of stack components, and anodic corrosion behavior of carbon materials.

Self-healing polymers---The importance of choosing an adequate healing monomer, and the olefin metathesis polymerization of agricultural oils

NASA Astrophysics Data System (ADS)

Mauldin, Timothy C.

Modern society's immense and ill-fated reliance on petrochemical-based polymeric materials will likely necessitate a shift in polymer production paradigms in the near future. The work presented herein attempts to address this issue via a two-pronged approach. First, efforts to improve the duration of composite materials by incorporation of a self-healing function are discussed, the fruitful application of which can potentially reduce or eliminate the massive carbon footprints associated with the repair/replacement of damaged materials. And second, polymeric materials derived predominately from natural and renewable feedstock---namely vegetable oils---are developed. Early microcapsule-based self-healing materials utilized dicyclopentadiene-filled microcapsules and Grubbs' olefin metathesis catalyst to initiate the healing mechanism. However, the patent-protected catalyst, made from the precious metal ruthenium and sometimes costly ligands, will likely never be inexpensive and therefore limit large-scale applications. Hence, clever approaches to reduce the healing catalyst loading in self-healing polymers are of great interest. To this end, our efforts have revolved around solving the problem of the relatively inefficient use of Grubbs' catalyst during the healing mechanism. Given that the mismatch of the olefin metathesis polymerization and Grubbs' catalyst dissolution (in monomer) kinetics is a known cause of this inefficient use of the catalyst, we attempted to tune the "latency" (i.e. pot life) of the olefin metathesis polymerization to ensure more complete dissolution of catalyst in monomer. In an alternative approach to improving efficient catalyst dissolution, we developed a simple model to predict relative dissolution rates of Grubbs' catalyst in a small library of healing monomers. This model was shown experimentally to be able to aid in the selection of, for example, reactive monomer additives that can yield impressive improvements in catalyst dissolution at small loadings. Furthermore, we have recently developed a novel rheokinetic technique designed to mimic the self-healing mechanism. This new analytical technique allows for collection of copious amounts of information related to the self-healing mechanism (e.g. healing kinetics, rheological and mechanical changes of polymerizing healing agents, adhesive interactions between healing agent and polymer matrix, etc.) to be extracted from a single experiment. New polymers derived from renewable feeds were synthesized via olefin metathesis polymerization techniques, which are ideally suited to react with the unactivated olefins (i.e. non-styrenic, non-acrylated, non-conjugated, etc.) prominent in most vegetable oils. Various vegetable oils were modified to contain norbornenyl functional groups via the high-pressure Diels-Alder addition of cyclopentadiene to their olefins to yield ROMP-reactive monomers. These monomers, polymerized in the presence of Grubbs' catalyst and the occasional comonomer, were able to yield highly crosslinked thermosets with ambient temperature storage moduli, glass transition temperatures and decomposition temperatures comparable to their currently-used, petrochemical-based counterparts. Other research thrusts in this area have focused on the development of renewable thermoplastic polymers. Vegetable oils were chemically modified to yield a series of alpha,o-dienes, from which polymers were formed via acyclic diene metathesis (ADMET). The resulting polymers were shown to have unique material properties, comparable to that of other biopolyesters (poly(lactic acid), poly(glycolides), poly(caprolactones), etc.) and common, petrochemical-derived polyesters.

Trends and structural shifts in health tourism: evidence from seasonal time-series data on health-related travel spending by Canada during 1970-2010.

PubMed

Loh, Chung-Ping A

2015-05-01

There has been a growing interest in better understanding the trends and determinants of health tourism activities. While much of the expanding literature on health tourism offers theoretical or qualitative discussion, empirical evidences has been lacking. This study employs Canada's outbound health tourism activities as an example to examine the trends in health tourism and its association with changing domestic health care market characteristics. A time-series model that accounts for potential structural changes in the trend is employed to analyze the quarterly health-related travel spending series reported in the Balance of Payments Statistics (BOPS) during 1970-2010 (n = 156). We identified a structural shift point which marks the start of an accelerated growth of health tourism and a flattened seasonality in such activities. We found that the health tourism activities of Canadian consumers increase when the private investment in medical facilities declines or when the private MPI increases during the years following the structural-change. We discussed the possible linkage of the structural shift to the General Agreement on Trade in Services (GATS), which went into effect in January, 1995. Copyright © 2015 Elsevier Ltd. All rights reserved.

Do neotropical migrant butterflies navigate using a solar compass?

PubMed

Oliveira; Srygley; Dudley

1998-12-01

Many tropical butterfly species are well-known for their migratory behaviour. Although these insects can maintain a constant direction throughout the day, the physiological mechanisms of orientation are unknown. It has been argued that tropical migrant butterflies must use a time-compensated sun compass to accomplish their journey, but the crucial experimental manipulations to test this hypothesis have not been conducted. This study reports the results of clock-shift experiments performed with two species of migrating butterflies (Pieridae: Aphrissa statira and Phoebis argante) captured during flight across Lake Gatun, Panama. The observed constant flight bearing of natural controls suggests that these species are capable of performing time-compensated celestial navigation. Our clock-shift experiments suggest that a sun compass is involved. Individuals submitted to a 4 h advance shift took significantly different mean orientations on release compared with control butterflies. The direction of this difference was consistent with the use of a sun compass. The magnitude was approximately half the predicted value if the vanishing bearing of released butterflies was used as the variable to evaluate the effect of time-shifting and approximately three-quarters of that predicted if the estimated heading was the variable used. Mean vanishing bearings of control and experimental butterflies did not correspond to predicted values. This difference can be attributed largely to the combined effects of wind and handling.

Advance concepts for the conversion of syngas liquids. Quarterly report {number_sign}5, October 30, 1995--January 31, 1996

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

Szostak, R.; Ingram, C.

Research efforts for the report period have been focused on the characterization of catalyst samples, mainly by ion exchange and spectroscopic techniques. Other activities included the preparation of more variants of the MeAPO-36 family containing various types and amounts of metals in their frameworks. Characterization of these samples by X-ray diffraction analysis was delayed due to malfunction of the Diffractometer since October of 1995. The instrument was back in working condition only since the ending of January and XRD analysis has resumed since then. Efforts from the research group were also concentrated on the preparation of manuscripts for publication. Workmore » in progress includes: synthesis of MnAPO5 and MgAPO5; synthesis of CoAPO5; chemical analysis; preliminary investigation of ion exchange capacities of zeolites; uptake kinetics on the Na-exchanged MnAPO5 and MgAPO5 with alkali and alkali earth metals.« less

Influence of copper on nickel-based catalysts in the conversion of glycerol

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

Miranda, Barbara C.; Chimentao, Ricardo J.; Szanyi, Janos

2015-05-01

The catalytic transformation of glycerol to value-added compounds was investigated over bimetallic Ni-Cu/γ-Al2O3 catalysts with Ni/Cu atomic ratios of 8/1, 4/1, 2/1, 1/1, 1/2, 1/4, and 1/8. XPS analysis revealed that the surface composition of the catalyst exhibited progressive enrichment of Cu as its content in the catalyst increased. H2-chemisorption indicated that the total number of exposed Ni atoms decreased as the Cu content increased. As a result, deep hydrogenolysis to produce CH4 was inhibited by the addition of Cu to the Ni catalyst, yielding higher selectivity towards the dehydration products of glycerol such as hydroxyacetone. FTIR spectra of adsorbedmore » CO reveals that Cu asserts both geometric and electronic effects on the adsorption properties of Ni. The geometrical effect is visualized by the progressive disappearance of the bridge-bound adsorbed CO on metallic Ni by the incorporation of Cu. This suggests that the deep hydrogenolysis of glycerol to CH4 formation requires an ensemble of adjacent active Ni atoms. The electronic effect of Cu on Ni is indicated by the red shift of the IR peak of adsorbed CO as the Cu content increases. The electronic interaction between Cu and Ni species was also substantiated by XANES results. HTREM revealed metal particles very well distributed on the support with particle size of 1.5 to 5 nm. The Ni-Cu samples were not a total intermetallic alloys. We also gratefully acknowledge the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division for the support of this work. The research related to the FTIR of adsorption of CO (Proposal 48209) was performed in the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE Office of Biological and Environmental Research located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle Memorial Institute under contract number DE-AC05-76RL01830.« less

Response of the microwave-induced cyclotron harmonic resistance spike to an in-plane magnetic field

NASA Astrophysics Data System (ADS)

Dai, Yanhua; Stone, Kristjan; Knez, Ivan; Zhang, Chi; Du, R. R.; Yang, Changli; Pfeiffer, L. N.; West, K. W.

2011-12-01

Microwave-induced resistance oscillations (MIROs) have been commonly observed in high-mobility GaAs/AlGaAs two-dimensional electron systems (2DESs) under microwave irradiation. In ultraclean GaAs/AlGaAs quantum wells, we have recently observed a very large resistance spike at the second harmonic of cyclotron resonance. In order to elucidate its origin, we have studied the response of microwave photoresistances in a two-axis magnetic field configuration, where the perpendicular (Bz) and the in-plane (Bx) components can be independently applied to the sample. The experiments reveal a distinctive response of the spike to the Bx compared with that of the MIROs. While the major MIRO peaks show an increasing phase shift toward a quarter period in increasing Bx, the spike position shows an essentially zero shift. This finding lends additional support for the notion that the spike is a unique effect in the microwave-driven 2DES.

Improved polar display technique of the phase angle of optical interference

NASA Astrophysics Data System (ADS)

Umeda, N.; Shirai, H.; Takasaki, H.

1984-02-01

A technique which displays the fractional order of optical interference by the azimuthal angle of radial arm has been improved by using a digital electronic circuit such as phase-locked loop and D flip-flop. The phase quadrature reference signals of this system are derived by reforming a reference signal and shifting it by a quarter wavelength referring to its waveform. As the result the orthogonal phase relation of the two signals is not affected by the frequency of the signal. This system has been proven to operate properly over the frequency range of 200-600 kHz without readjusting the electric system.

Strategies for navigating the healthcare credit market.

PubMed

Wareham, T L

2001-04-01

Not-for-profit healthcare organizations are experiencing a tightened credit market due to financial stresses on the healthcare industry such as declining payments, effects of the Balanced Budget Act of 1997, and the shift to outpatient care. In the future, healthcare organizations wanting to access the capital market will be expected to preserve cash as an "insurance policy," offer greater security and stricter covenants, and report financial information on a quarterly basis. To meet these requirements and navigate today's tighter credit market, healthcare financial managers will need to focus on the organization's most reliably profitable areas of business, link strategic and financial issues, and carefully monitor the balance sheet.

Building a Science of Animal Minds: Lloyd Morgan, Experimentation, and Morgan's Canon.

PubMed

Fitzpatrick, Simon; Goodrich, Grant

2017-08-01

Conwy Lloyd Morgan (1852-1936) is widely regarded as the father of modern comparative psychology. Yet, Morgan initially had significant doubts about whether a genuine science of comparative psychology was even possible, only later becoming more optimistic about our ability to make reliable inferences about the mental capacities of non-human animals. There has been a fair amount of disagreement amongst scholars of Morgan's work about the nature, timing, and causes of this shift in Morgan's thinking. We argue that Morgan underwent two quite different shifts of attitude towards the proper practice of comparative psychology. The first was a qualified acceptance of the Romanesian approach to comparative psychology that he had initially criticized. The second was a shift away from Romanes' reliance on systematizing anecdotal evidence of animal intelligence towards an experimental approach, focused on studying the development of behaviour. We emphasize the role of Morgan's evolving epistemological views in bringing about the first shift - in particular, his philosophy of science. We emphasize the role of an intriguing but overlooked figure in the history of comparative psychology in explaining the second shift, T. Mann Jones, whose correspondence with Morgan provided an important catalyst for Morgan's experimental turn, particularly the special focus on development. We also shed light on the intended function of Morgan's Canon, the methodological principle for which Morgan is now mostly known. The Canon can only be properly understood by seeing it in the context of Morgan's own unique experimental vision for comparative psychology.

Tuning the properties of copper-based catalysts based on molecular in situ studies of model systems.

PubMed

Stacchiola, Darío J

2015-07-21

Studying catalytic processes at the molecular level is extremely challenging, due to the structural and chemical complexity of the materials used as catalysts and the presence of reactants and products in the reactor's environment. The most common materials used on catalysts are transition metals and their oxides. The importance of multifunctional active sites at metal/oxide interfaces has been long recognized, but a molecular picture of them based on experimental observations is only recently emerging. The initial approach to interrogate the surface chemistry of catalysts at the molecular level consisted of studying metal single crystals as models for reactive metal centers, moving later to single crystal or well-defined thin film oxides. The natural next iteration consisted in the deposition of metal nanoparticles on well-defined oxide substrates. Metal nanoparticles contain undercoordinated sites, which are more reactive. It is also possible to create architectures where oxide nanoparticles are deposited on top of metal single crystals, denominated inverse catalysts, leading in this case to a high concentration of reactive cationic sites in direct contact with the underlying fully coordinated metal atoms. Using a second oxide as a support (host), a multifunctional configuration can be built in which both metal and oxide nanoparticles are located in close proximity. Our recent studies on copper-based catalysts are presented here as an example of the application of these complementary model systems, starting from the creation of undercoordinated sites on Cu(111) and Cu2O(111) surfaces, continuing with the formation of mixed-metal copper oxides, the synthesis of ceria nanoparticles on Cu(111) and the codeposition of Cu and ceria nanoparticles on TiO2(110). Catalysts have traditionally been characterized before or after reactions and analyzed based on static representations of surface structures. It is shown here how dynamic changes on a catalyst's chemical state and morphology can be followed during a reaction by a combination of in situ microscopy and spectroscopy. In addition to determining the active phase of a catalyst by in situ methods, the presence of weakly adsorbed surface species or intermediates generated only in the presence of reactants can be detected, allowing in turn the comparison of experimental results with first principle modeling of specific reaction mechanisms. Three reactions are used to exemplify the approach: CO oxidation (CO + 1/2O2 → CO2), water gas shift reaction (WGSR) (CO + H2O → CO2 + H2), and methanol synthesis (CO2 + 3H2 → CH3OH + H2O). During CO oxidation, the full conversion of Cu(0) to Cu(2+) deactivates an initially outstanding catalyst. This can be remedied by the formation of a TiCuOx mixed-oxide that protects the presence of active partially oxidized Cu(+) cations. It is also shown that for the WGSR a switch occurs in the reaction mechanism, going from a redox process on Cu(111) to a more efficient associative pathway at the interface of ceria nanoparticles deposited on Cu(111). Similarly, the activation of CO2 at the ceria/Cu(111) interface allows its facile hydrogenation to methanol. Our combined studies emphasize the need of searching for optimal metal/oxide interfaces, where multifunctional sites can lead to new efficient catalytic reaction pathways.

Duration of time on shift before accidental blood or body fluid exposure for housestaff, nurses, and technicians.

PubMed

Green-McKenzie, Judith; Shofer, Frances S

2007-01-01

Shift work has been found to be associated with an increased rate of errors and accidents among healthcare workers (HCWs), but the effect of shift work on accidental blood and body fluid exposure sustained by HCWs has not been well characterized. To determine the duration of time on shift before accidental blood and body fluid exposure in housestaff, nurses, and technicians and the proportion of housestaff who sustain a blood and body fluid exposure after 12 hours on duty. This retrospective, descriptive study was conducted during a 24-month period at a large urban teaching hospital. Participants were HCWs who sustained an accidental blood and body fluid exposure. Housestaff were on duty significantly longer than both nursing staff (P=.02) and technicians (P<.0001) before accidental blood and body fluid exposure. Half of the blood and body fluid exposures sustained by housestaff occurred after being on duty 8 hours or more, and 24% were sustained after being on duty 12 hours or more. Of all HCWs, 3% reported an accidental blood and body fluid exposure, with specific rates of 7.9% among nurses, 9.4% among housestaff, and 3% among phlebotomists. Housestaff were significantly more likely to have longer duration of time on shift before blood and body fluid exposure than were the other groups. Almost one-quarter of accidental blood and body fluid exposures to housestaff were incurred after they had been on duty for 12 hours or more. Housestaff sustained a higher rate of accidental blood and body fluid exposures than did nursing staff and technicians.

Valorization of food waste into hydroxymethylfurfural: Dual role of metal ions in successive conversion steps.

PubMed

Yu, Iris K M; Tsang, Daniel C W; Yip, Alex C K; Chen, Season S; Ok, Yong Sik; Poon, Chi Sun

2016-11-01

This study aimed to transform food waste into a value-added chemical, hydroxymethylfurfural (HMF), and unravel the tangled effects induced by the metal catalysts on each single step of the successive conversion pathway. The results showed that using cooked rice and bread crust as surrogates of starch-rich food waste, yields of 8.1-9.5% HMF and 44.2-64.8% glucose were achieved over SnCl4 catalyst. Protons released from metal hydrolysis and acidic by-products rendered Brønsted acidity to catalyze fructose dehydration and hydrolysis of glycosidic bond. Lewis acid site of metals could facilitate both fructose dehydration and glucose isomerization via promoting the rate-limiting internal hydride shift, with the catalytic activity determined by its electronegativity, electron configuration, and charge density. Lewis acid site of a higher valence also enhanced hydrolysis of polysaccharide. However, the metals also catalyzed undesirable polymerization possibly by polarizing the carbonyl groups of sugars and derivatives, which should be minimized by process optimization. Copyright © 2016 Elsevier Ltd. All rights reserved.

Water dissociation and CO oxidation over Au/anatase catalyst. A DFT-D2 study

NASA Astrophysics Data System (ADS)

Saqlain, Muhammad Adnan; Hussain, Akhtar; Siddiq, Muhammad; Leitão, Alexandre A.

2018-03-01

With the help of DFT-D2 methodology, we have investigated the adsorption of water on clean anatase(001) and Au/anatase(001). In the former case, adsorption energies of H2O differ to small extent computed employing GGA = PW91 and DFT-D2 methods. While the GGA = PW91 predicts that water would desorb close to 650 K on the TiO2 surface, the DFT-D2 predicts that desorption is most likely to occur above 700 K. A comparison of water adsorption on TiO2 and Au/TiO2 surfaces shows that the TiO2 prefers dimer adsorption whereas the Au/TiO2 prefers monomer adsorption. We found that the diffusion of surface hydroxyls on to the Au cluster from the Au/TiO2 periphery is unlikely and it seems that the CO oxidation would occur at the Au/TiO2 boundary. The results show that water dissociation and CO oxidation steps occur easily on Au/TiO2 indicating that this could be good alternative catalyst for water gas shift reaction industry.

Surface-Cross-Linked Micelles as Multifunctionalized Organic Nanoparticles for Controlled Release, Light Harvesting, and Catalysis

PubMed Central

2016-01-01

Surfactant micelles are dynamic entities with a rapid exchange of monomers. By “clicking” tripropargylammonium-containing surfactants with diazide cross-linkers, we obtained surface-cross-linked micelles (SCMs) that could be multifunctionalized for different applications. They triggered membrane fusion through tunable electrostatic interactions with lipid bilayers. Antenna chromophores could be installed on them to create artificial light-harvesting complexes with efficient energy migration among tens to hundreds of chromophores. When cleavable cross-linkers were used, the SCMs could break apart in response to redox or pH signals, ejecting entrapped contents quickly as a result of built-in electrostatic stress. They served as caged surfactants whose surface activity was turned on by environmental stimuli. They crossed cell membranes readily. Encapsulated fluorophores showed enhanced photophysical properties including improved quantum yields and greatly expanded Stokes shifts. Catalytic groups could be installed on the surface or in the interior, covalently attached or physically entrapped. As enzyme mimics, the SCMs enabled rational engineering of the microenvironment around the catalysts to afford activity and selectivity not possible with conventional catalysts. PMID:27181610

Synthesis and electrochemical characterization of Ti{sub x}Ta{sub y}Al{sub z}N{sub 1-δ}O{sub γ} for fuel cell catalyst supports

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

Wakabayashi, Ryo H.; Abruña, Héctor D., E-mail: hda1@cornell.edu; DiSalvo, Francis J., E-mail: fjd3@cornell.edu

2017-02-15

Quinary Ti{sub x}Ta{sub y}Al{sub z}N{sub 1-δ}O{sub γ} of various compositions have been prepared by a co-precipitation method followed by ammonolysis. The nitride samples were examined as potential catalyst supports in polymer electrolyte membrane fuel cells. The nitride products crystallized in the rock salt (NaCl) structure over a wide range of compositions. The addition of Ta and Al was highly beneficial towards improving the chemical and electrochemical stability of TiN, without a significant loss of electrical conductivity. Platinum particles were successfully deposited on the (oxy)nitride samples, and the composite samples at some compositions were found to be comparable to Pt/carbon inmore » their stability and catalytic activity even without optimizing the Pt deposition and dispersion processes. - Graphical abstract: The effect of additions of Ta and Al into TiN structure. Shifts the lattice constant, and increases its chemical stability in acidic environment.« less

Diversity of Secondary Structure in Catalytic Peptides with β-Turn-Biased Sequences

PubMed Central

2016-01-01

X-ray crystallography has been applied to the structural analysis of a series of tetrapeptides that were previously assessed for catalytic activity in an atroposelective bromination reaction. Common to the series is a central Pro-Xaa sequence, where Pro is either l- or d-proline, which was chosen to favor nucleation of canonical β-turn secondary structures. Crystallographic analysis of 35 different peptide sequences revealed a range of conformational states. The observed differences appear not only in cases where the Pro-Xaa loop-region is altered, but also when seemingly subtle alterations to the flanking residues are introduced. In many instances, distinct conformers of the same sequence were observed, either as symmetry-independent molecules within the same unit cell or as polymorphs. Computational studies using DFT provided additional insight into the analysis of solid-state structural features. Select X-ray crystal structures were compared to the corresponding solution structures derived from measured proton chemical shifts, 3J-values, and 1H–1H-NOESY contacts. These findings imply that the conformational space available to simple peptide-based catalysts is more diverse than precedent might suggest. The direct observation of multiple ground state conformations for peptides of this family, as well as the dynamic processes associated with conformational equilibria, underscore not only the challenge of designing peptide-based catalysts, but also the difficulty in predicting their accessible transition states. These findings implicate the advantages of low-barrier interconversions between conformations of peptide-based catalysts for multistep, enantioselective reactions. PMID:28029251

Visible and near-infrared photothermal catalyzed hydrogenation of gaseous CO 2 over nanostructured Pd@Nb 2O 5

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

Jia, Jia; O'Brien, Paul G.; He, Le

2016-07-05

The reverse water gas shift (RWGS) reaction driven by Nb 2O 5 nanorod-supported Pd nanocrystals without external heating using visible and near infrared (NIR) light is demonstrated. By measuring the dependence of the RWGS reaction rates on the intensity and spectral power distribution of filtered light incident onto the nanostructured Pd@Nb 2O 5 catalyst, it is determined that the RWGS reaction is activated photothermally. That is the RWGS reaction is initiated by heat generated from thermalization of charge carriers in the Pd nanocrystals that are excited by interband and intraband absorption of visible and NIR light. Taking advantage of thismore » photothermal effect, a visible and NIR responsive Pd@Nb 2O 5 hybrid catalyst that efficiently hydrogenates CO 2 to CO at an impressive rate as high as 1.8 mmol gcat –1 h –1 is developed. The mechanism of this photothermal reaction involves H 2 dissociation on Pd nanocrystals and subsequent spillover of H to the Nb 2O 5 nanorods whereupon adsorbed CO 2 is hydrogenated to CO. Here, this work represents a significant enhancement in our understanding of the underlying mechanism of photothermally driven CO 2 reduction and will help guide the way toward the development of highly efficient catalysts that exploit the full solar spectrum to convert gas-phase CO 2 to valuable chemicals and fuels.« less

Microbial disinfection of water with endotoxin degradation by photocatalysis using Ag@TiO2 core shell nanoparticles.

PubMed

S, Sreeja; K, Vidya Shetty

2016-09-01

The studies on photocatalytic disinfection of water contaminated with Escherichia coli using Ag core and TiO2 shell (Ag@TiO2) nanoparticles under UV irradiation showed that these nanoparticles are very efficient in water disinfection both in their free and immobilised form. Complete disinfection of 40 × 10(8) CFU/mL could be achieved in 60 min with 0.4 g/L catalyst loading and in 35 min with 1 g/L catalyst loading. Ag@TiO2 nanoparticles were found to be superior to TiO2 nanoparticles in photocatalytic disinfection of water. Kinetics of disinfection followed Chick's law, and the pseudo-first-order rate constant was 0.0168 min(-1) for a catalyst loading of 0.1 g/L. Disinfection of water and degradation of endotoxins (harmful disinfection residual) occurred simultaneously during photocatalysis thereby making the treated water safe for use. Endotoxin degradation showed a shifting order of kinetics. The rate of photocatalysis with nanoparticles immobilised in cellulose acetate film was marginally lower as compared to that of free nanoparticles. Negligible Ag ion leakage and re-growth of cells post-photo-catalytic treatment of water confirmed that complete disintegration of E. coli occurred during photocatalysis making the treated water safe for use. Therefore, Ag@TiO2 nanoparticles have a potential for large-scale application in drinking water treatment plants and household purification units.

Photodegradation of microcystin-LR catalyzed by metal phthalocyanines immobilized on TiO2-SiO2 under visible-light irradiation.

PubMed

Peng, Guotao; Fan, Zhengqiu; Wang, Xiangrong; Sui, Xin; Chen, Chen

2015-01-01

Microcystins (MCs) are a group of monocyclic heptapeptide toxins produced by species of cyanobacteria. Since MCs exhibit acute and chronic effects on humans and wildlife by damaging the liver, they are of increasing concern worldwide. In this study, we investigated the ability of the phthalocyanine compound (ZnPc-TiO2-SiO2) to degrade microcystin-LR (MC-LR) in the presence of visible light. X-ray diffraction (XRD) and UV-Visible diffuse reflectance spectra (UV-Vis DRS) were utilized to characterize the crystalline phase and the absorption behavior of this catalyst. According to the results, XRD spectra of ZnPc-TiO2-SiO2 powders taken in the 2θ configuration exhibited the peaks characteristic of the anatase phase. UV-Vis DRS showed that the absorption band wavelength shifted to the visible range when ZnPc was supported on the surface of TiO2-SiO2. Subsequently, several parameters including catalyst dose, MC-LR concentrations and pH were investigated. The MC-LR was quantified in each sample through high-performance liquid chromatography (HPLC). The maximum MC-LR degradation rate of 80.2% can be obtained within 300 minutes under the following conditions: catalyst dose of 7.50 g/L, initial MC-LR concentration of 17.35 mg/L, pH 6.76 and the first cycling run of the photocatalytic reaction. Moreover, the degradation process fitted well with the pseudo-first-order kinetic model.

LROC Investigation of Three Strategies for Reducing the Impact of Respiratory Motion on the Detection of Solitary Pulmonary Nodules in SPECT

NASA Astrophysics Data System (ADS)

Smyczynski, Mark S.; Gifford, Howard C.; Dey, Joyoni; Lehovich, Andre; McNamara, Joseph E.; Segars, W. Paul; King, Michael A.

2016-02-01

The objective of this investigation was to determine the effectiveness of three motion reducing strategies in diminishing the degrading impact of respiratory motion on the detection of small solitary pulmonary nodules (SPNs) in single-photon emission computed tomographic (SPECT) imaging in comparison to a standard clinical acquisition and the ideal case of imaging in the absence of respiratory motion. To do this nonuniform rational B-spline cardiac-torso (NCAT) phantoms based on human-volunteer CT studies were generated spanning the respiratory cycle for a normal background distribution of Tc-99 m NeoTect. Similarly, spherical phantoms of 1.0-cm diameter were generated to model small SPN for each of the 150 uniquely located sites within the lungs whose respiratory motion was based on the motion of normal structures in the volunteer CT studies. The SIMIND Monte Carlo program was used to produce SPECT projection data from these. Normal and single-lesion containing SPECT projection sets with a clinically realistic Poisson noise level were created for the cases of 1) the end-expiration (EE) frame with all counts, 2) respiration-averaged motion with all counts, 3) one fourth of the 32 frames centered around EE (Quarter Binning), 4) one half of the 32 frames centered around EE (Half Binning), and 5) eight temporally binned frames spanning the respiratory cycle. Each of the sets of combined projection data were reconstructed with RBI-EM with system spatial-resolution compensation (RC). Based on the known motion for each of the 150 different lesions, the reconstructed volumes of respiratory bins were shifted so as to superimpose the locations of the SPN onto that in the first bin (Reconstruct and Shift). Five human observers performed localization receiver operating characteristics (LROC) studies of SPN detection. The observer results were analyzed for statistical significance differences in SPN detection accuracy among the three correction strategies, the standard acquisition, and the ideal case of the absence of respiratory motion. Our human-observer LROC determined that Quarter Binning and Half Binning strategies resulted in SPN detection accuracy statistically significantly below ( ) that of standard clinical acquisition, whereas the Reconstruct and Shift strategy resulted in a detection accuracy not statistically significantly different from that of the ideal case. This investigation demonstrates that tumor detection based on acquisitions associated with less than all the counts which could potentially be employed may result in poorer detection despite limiting the motion of the lesion. The Reconstruct and Shift method results in tumor detection that is equivalent to ideal motion correction.

Adequation between environmental shifts and human speciations during the Plio-PleistoceneAdéquation entre changements environnementaux et spéciations humaines au Plio-Pléistocène

NASA Astrophysics Data System (ADS)

Zeitoun, Valery

2000-01-01

Several synthetic studies provide evidence of faunistic and floristic shifts as consequences of global climatic events around 2.5 and 1.8 Ma. Some authors are more confident in the role played by local tectonic events to explain such a change in terms of vicariance. It is possible that astronomic, tectonic and climatic variations are linked, as the lithosphere is a catalyst for biosphere more or less strong according to the period. The purpose of this paper is to confront independent environmental and anatomical data to try to understand the evolutionary process in hominids, with particular emphasis on species of the genus Homo in East Africa during the Plio-Pleistocene period. Thus the result of a cladistic analysis based on 35 Otus and 468 features of the calvaria is showing the onset of at least four species to describe the grade of Homo habilis, living in East Africa. The radiation is congruent with the contemporaneous environmental shifts around 2.5 Ma, as is also the case for bovids or cercopithecids. Some Homo erectus left Africa when another climatic pulse happened around 1.8 Ma.

Morphology and the gradient of a symmetric potential predict gait transitions of dogs.

PubMed

Wilshin, Simon; Haynes, G Clark; Porteous, Jack; Koditschek, Daniel; Revzen, Shai; Spence, Andrew J

2017-08-01

Gaits and gait transitions play a central role in the movement of animals. Symmetry is thought to govern the structure of the nervous system, and constrain the limb motions of quadrupeds. We quantify the symmetry of dog gaits with respect to combinations of bilateral, fore-aft, and spatio-temporal symmetry groups. We tested the ability of symmetries to model motion capture data of dogs walking, trotting and transitioning between those gaits. Fully symmetric models performed comparably to asymmetric with only a [Formula: see text] increase in the residual sum of squares and only one-quarter of the parameters. This required adding a spatio-temporal shift representing a lag between fore and hind limbs. Without this shift, the symmetric model residual sum of squares was [Formula: see text] larger. This shift is related to (linear regression, [Formula: see text], [Formula: see text]) dog morphology. That this symmetry is respected throughout the gaits and transitions indicates that it generalizes outside a single gait. We propose that relative phasing of limb motions can be described by an interaction potential with a symmetric structure. This approach can be extended to the study of interaction of neurodynamic and kinematic variables, providing a system-level model that couples neuronal central pattern generator networks and mechanical models.

Differential Dynamic Engagement within 24 SH3 Domain: Peptide Complexes Revealed by Co-Linear Chemical Shift Perturbation Analysis

PubMed Central

Stollar, Elliott J.; Lin, Hong; Davidson, Alan R.; Forman-Kay, Julie D.

2012-01-01

There is increasing evidence for the functional importance of multiple dynamically populated states within single proteins. However, peptide binding by protein-protein interaction domains, such as the SH3 domain, has generally been considered to involve the full engagement of peptide to the binding surface with minimal dynamics and simple methods to determine dynamics at the binding surface for multiple related complexes have not been described. We have used NMR spectroscopy combined with isothermal titration calorimetry to comprehensively examine the extent of engagement to the yeast Abp1p SH3 domain for 24 different peptides. Over one quarter of the domain residues display co-linear chemical shift perturbation (CCSP) behavior, in which the position of a given chemical shift in a complex is co-linear with the same chemical shift in the other complexes, providing evidence that each complex exists as a unique dynamic rapidly inter-converting ensemble. The extent the specificity determining sub-surface of AbpSH3 is engaged as judged by CCSP analysis correlates with structural and thermodynamic measurements as well as with functional data, revealing the basis for significant structural and functional diversity amongst the related complexes. Thus, CCSP analysis can distinguish peptide complexes that may appear identical in terms of general structure and percent peptide occupancy but have significant local binding differences across the interface, affecting their ability to transmit conformational change across the domain and resulting in functional differences. PMID:23251481

Novel Au-TiC Catalysts for CO Oxidation and Desulfurization Processes

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

Rodriguez, J.A.; Liu, P.; Takahashi, Y.

2011-05-30

Recent articles dealing with the physical and chemical properties of novel Au-TiC catalysts are reviewed. High-resolution photoemission, scanning tunneling microscopy and first-principles periodic density-functional calculations were used to study the deposition of gold on a TiC(0 0 1) surface. Gold grows forming two-dimensional (very low coverage) and three-dimensional (medium and large coverage) islands on the carbide substrate. A positive shift in the binding energy of the C 1s core level is observed after the deposition of Au on TiC(0 0 1). The results of the density-functional calculations corroborate the formation of Au-C bonds. In general, the bond between Au andmore » the TiC(0 0 1) surface exhibits very little ionic character, but there is a substantial polarization of electrons around Au that facilitates bonding of the adatoms with electron-acceptor molecules (CO, O{sub 2}, C{sub 2}H{sub 4}, SO{sub 2}, thiophene, etc.). Experimental measurements indicate that Au/TiC(0 0 1) is a very good catalysts for the oxidation of CO, the destruction of SO{sub 2} and the hydrodesulfurization of thiophene. At temperatures below 200 K, Au/TiC(0 0 1) is able to perform the 2CO + O{sub 2} {yields} 2CO{sub 2} reaction and the full decomposition of SO{sub 2}. Furthermore, in spite of the very poor hydrodesulfurization performance of TiC(0 0 1) or Au(1 1 1), a Au/TiC(0 0 1) surface displays a hydrodesulfurization activity higher than that of conventional Ni/MoS{sub x} catalysts. Metal carbides are excellent supports for enhancing the chemical reactivity of gold. The Au/TiC system is more chemically active than systems generated by depositing Au nanoparticles on oxide surfaces.« less

Novel Au-TiC Catalysts for CO Oxidation and Desulfurization Processes

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

J Rodriguez; P Liu; Y Takahashi

2011-12-31

Recent articles dealing with the physical and chemical properties of novel Au-TiC catalysts are reviewed. High-resolution photoemission, scanning tunneling microscopy and first-principles periodic density-functional calculations were used to study the deposition of gold on a TiC(0 0 1) surface. Gold grows forming two-dimensional (very low coverage) and three-dimensional (medium and large coverage) islands on the carbide substrate. A positive shift in the binding energy of the C 1s core level is observed after the deposition of Au on TiC(0 0 1). The results of the density-functional calculations corroborate the formation of Au-C bonds. In general, the bond between Au andmore » the TiC(0 0 1) surface exhibits very little ionic character, but there is a substantial polarization of electrons around Au that facilitates bonding of the adatoms with electron-acceptor molecules (CO, O{sub 2}, C{sub 2}H{sub 4}, SO{sub 2}, thiophene, etc.). Experimental measurements indicate that Au/TiC(0 0 1) is a very good catalysts for the oxidation of CO, the destruction of SO{sub 2} and the hydrodesulfurization of thiophene. At temperatures below 200 K, Au/TiC(0 0 1) is able to perform the 2CO + O{sub 2} {yields} 2CO{sub 2} reaction and the full decomposition of SO{sub 2}. Furthermore, in spite of the very poor hydrodesulfurization performance of TiC(0 0 1) or Au(1 1 1), a Au/TiC(0 0 1) surface displays a hydrodesulfurization activity higher than that of conventional Ni/MoS{sub x} catalysts. Metal carbides are excellent supports for enhancing the chemical reactivity of gold. The Au/TiC system is more chemically active than systems generated by depositing Au nanoparticles on oxide surfaces.« less

Synthesis and Characterization of Platinum-Ruthenium-Tin Catalysts

NASA Astrophysics Data System (ADS)

Uffalussy, Karen

Magnesia-supported trimetallic Pt-Ru-Sn catalysts prepared through a cluster and a conventional synthetic route have been investigated in terms of their structural properties and their catalytic activity for the hydrogenation of citral and crotonaldehyde. FTIR results indicate that the majority of the stabilizing ligands remain attached to the PtRu5(μ-SnPh 2)(C)(CO)15 cluster used following impregnation onto the MgO support. Under H2 reduction conditions, partial and full ligand removal are both observed at 473 and 573 K, respectively. HRSTEM analysis shows that cluster-derived samples exhibit significantly smaller average metal particle sizes, as well as narrower particle size distributions than the corresponding conventionally prepared ones. EDX measurements show that in the cluster-derived catalysts, the majority of the metal particles present are trimetallic in nature, with metal compositions similar to those of the original cluster. In contrast, the conventionally prepared materials contain mostly bimetallic and monometallic particles with variable compositions. XPS was used to determine how the variation in method of Sn addition to bimetallic Pt-Ru affects the electronic state for the trimetallic Pt-Ru-Sn/MgO system prepared by impregnation using multimetallic clusters, metal-salts, and the combination of both precursor types. Results show that the PtRu5Sn/MgO material has a significantly higher percentage of Sn0 in comparison to Pt-Ru-Sn/MgO and PtRu5-Sn/MgO, and a corresponding shift in both Pt and Ru peaks can be correlated to this relative change in Sn oxidation state. The formation of smaller metal particles and electronic modification of Pt and Ru by Sn in the cluster-derived catalysts and the presence of the three metals in these particles in close proximity result in higher activity and selectivity to the unsaturated alcohols for the hydrogenation of both citral and crotonaldehyde.

Investigation of Silica-Supported Vanadium Oxide Catalysts by High-Field 51 V Magic-Angle Spinning NMR

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

Jaegers, Nicholas R.; Wan, Chuan; Hu, Mary Y.

Supported V2O5/SiO2 catalysts were studied using solid state 51V MAS NMR at a sample spinning rate of 36 kHz and at a magnetic field of 19.975 T for a better understanding of the coordination of the vanadium oxide as a function of environmental conditions . Structural transformations of the supported vanadium oxide species between the catalyst in the dehydrated state and hydrated state under an ambient environment were revisited to examine the degree of oligomerization and the effect of water. The experimental results indicate the existence of a single dehydrated surface vanadium oxide species that resonates at -675 ppm andmore » two vanadium oxide species under ambient conditions that resonate at -566 and -610 ppm, respectively. No detectable structural difference was found as a function of vanadium oxide loading on SiO2 (3% V2O5/SiO2 and 8% V2O5/SiO2). Quantum chemistry simulations of the 51V NMR chemical shifts on predicted surface structures were used as an aide in understanding potential surface vanadium oxide species on the silica support. The results suggest the formation of isolated surface VO4 units for the dehydrated catalysts with the possibility of dimer and cyclic trimer presence. The absence of bridging V-O-V vibrations (~200-300 cm-1) in the Raman spectra [Gao et al. J. Phys. Chem. B 1998, 102, 10842-10852], however, indicates that the isolated surface VO4 sites are the dominant dehydrated surface vanadia species on silica. Upon exposure to water, hydrolysis of the bridging V-O-Si bonds is most likely responsible for the decreased electron shielding experienced by vanadium. No indicators for the presence of hydrated decavanadate clusters or hydrated vanadia gels previously proposed in the literature were detected in this study.« less

Effects of indium contents on photocatalytic performance of ZnIn{sub 2}S{sub 4} for hydrogen evolution under visible light

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

Song, Kelin; Zhu, Rongshu, E-mail: rszhu@hitsz.edu.cn; Public Platform for Technological Service in Urban Waste Reuse and Energy Regeneration, Shenzhen 518055

2015-12-15

A series of ZnIn{sub x}S{sub 4+y} (x=1.6, 2.0, 2.3, 2.6, 2.9, 3.1) photocatalysts were synthesized via a facile hydrothermal method and characterized by various analytical techniques, such as XRD, EDS, UV–vis DRS, SEM, TEM, BET and PL. The ZnIn{sub x}S{sub 4+y} photocatalysts had a similar crystal structure. With the increase of indium content, the absorption edges of ZnIn{sub x}S{sub 4+y} photocatalysts shifted to longer wavelength, their crystal sizes decreased firstly and then increased and the variation of the specific surface area and total pore volume was exactly opposite. Especially, when x=2.3, ZnIn{sub 2.3}S{sub 4+y} catalyst had smallest crystal size, largestmore » specific surface area and total pore volume. Additionally, the morphology of ZnIn{sub x}S{sub 4+y} greatly depended on the contents of indium. The photocatalytic activity of ZnIn{sub x}S{sub 4+y} was evaluated by photocatalytic hydrogen production from water under visible light. The ZnIn{sub 2.3}S{sub 4+y} sample had the highest photocatalytic activity among these ZnIn{sub x}S{sub 4+y} photocatalysts and its hydrogen production rate was 363 μmol/g h. - Graphical abstract: First, a series of catalysts were synthesized. And then those were characterized by various analytical techniques (such as SEM). finally, The photocatalytic activity of catalyst was evaluated by photocatalytic hydrogen production from water under visible light. - Highlights: • The photocatalytic property was studied upon visible-light irradiation. • ZnIn{sub x}S{sub 4+y} photocatalysts show superior photocatalytic activity. • The catalyst of grain size, morphology and BET are related to indium content. • ZnIn{sub x}S{sub 4+y} photocatalysts were synthesized via a facile hydrothermal method.« less

Characterization and photocatalytic performance evaluation of various metal ion-doped microstructured TiO2 under UV and visible light.

PubMed

Sahoo, Chittaranjan; Gupta, Ashok K

2015-01-01

Commercially available microcrystalline TiO2 was doped with silver, ferrous and ferric ion (1.0 mol %) using silver nitrate, ferrous sulfate and ferric nitrate solutions following the liquid impregnation technology. The catalysts prepared were characterised by FESEM, XRD, FTIR, DRS, particle size and micropore analysis. The photocatalytic activity of the prepared catalysts was tested on the degradation of two model dyes, methylene blue (3,7-bis (Dimethylamino)-phenothiazin-5-ium chloride, a cationic thiazine dye) and methyl blue (disodium;4-[4-[[4-(4-sulfonatoanilino)phenyl]-[4-(4-sulfonatophenyl)azaniumylidenecyclohexa-2,5-dien-1-ylidene]methyl]anilino]benzene sulfonate, an anionic triphenyl methane dye) under irradiation by UV and visible light in a batch reactor. The efficiency of the photocatalysts under UV and visible light was compared to ascertain the light range for effective utilization. The catalysts were found to have the anatase crystalline structure and their particle size is in a range of 140-250 nm. In the case of Fe(2+) doped TiO2 and Fe(3+) doped TiO2, there was a greater shift in the optical absorption towards the visible range. Under UV light, Ag(+) doped TiO2 was the most efficient catalyst and the corresponding decolorization was more than 99% for both the dyes. Under visible light, Fe(3+) doped TiO2 was the most efficient photocatalyst with more than 96% and 90% decolorization for methylene blue and methyl blue, respectively. The kinetics of the reaction under both UV and visible light was investigated using the Langmuir-Hinshelwood pseudo-first-order kinetic model. Kinetic measurements confirmed that, Ag(+) doped TiO2 was most efficient in the UV range, while Fe(3+) doped TiO2 was most efficient in the visible range.

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

Probing the surface of γ-Al2O3 by oxygen-17 dynamic nuclear polarization enhanced solid-state NMR spectroscopy.

PubMed

Li, Wenzheng; Wang, Qiang; Xu, Jun; Aussenac, Fabien; Qi, Guodong; Zhao, Xingling; Gao, Pan; Wang, Chao; Deng, Feng

2018-06-14

γ-Al2O3 is an important catalyst and catalyst support of industrial interest. Its acid/base characteristics are correlated to the surface structure, which has always been an issue of concern. In this work, the complex (sub-)surface oxygen species on surface-selectively labelled γ-Al2O3 were probed by 17O dynamic nuclear polarization surface-enhanced NMR spectroscopy (DNP-SENS). Direct 17O MAS and indirect 1H-17O cross-polarization (CP)/MAS DNP experiments enable observation of the (sub-)surface bare oxygen species and hydroxyl groups. In particular, a two-dimensional (2D) 17O 3QMAS DNP spectrum was for the first time achieved for γ-Al2O3, in which two O(Al)4 and one O(Al)3 bare oxygen species were identified. The 17O isotropic chemical shifts (δcs) vary from 56.7 to 81.0 ppm and the quadrupolar coupling constants (CQ) range from 0.6 to 2.5 MHz for the three oxygen species. The coordinatively unsaturated O(Al)3 species is characterized by a higher field chemical shift (56.7 ppm) and the largest CQ value (2.5 MHz) among these oxygen sites. 2D 1H → 17O HETCOR DNP experiments allow us to discriminate three bridging (Aln)-μ2-OH and two terminal (Aln)-μ1-OH hydroxyl groups. The structural features of the bare oxygen species and hydroxyl groups are similar for the γ-Al2O3 samples isotopically labelled by 17O2 gas or H217O. The results presented here show that the combination of surface-selective labelling and DNP-SENS is an effective approach for characterizing oxides with complex surface species.

Characterization of N,C-codoped TiO 2 films prepared by reactive DC magnetron sputtering

NASA Astrophysics Data System (ADS)

Wu, Kee-Rong; Hung, Chung-Hsuang

2009-12-01

Titanium dioxide (TiO 2) films are deposited by codoping nitrogen and carbon on indium tin oxide-coated substrates as visible light (Vis)-enabled catalysts. The X-ray diffraction peak intensity of the preferential orientation in (2 1 1) plane declines when the topmost 1.0 μm layer of the film is ground off. The decrease in the crystallite size and the crystallinity of anatase TiO 2 film is also evidenced by a shift towards the high wave number and broadening of the Raman spectra. Low doping concentrations of N (1.3%) and C (1.8%) are estimated by X-ray photoelectron spectroscopy (XPS) which displays an N 1 s peak at 396.8 eV and a C 1 s peak at 282.1 eV, respectively. This is attributed to the substitution of the oxygen sites with nitrogen and carbon, which is believed to be responsible for the Vis photocatalytic activity into a wavelength of >500 nm. The cross-sectional transmission electron microscopy images show larger pores at the grain boundaries and in larger columnar crystals than in the undoped TiO 2 film. All of these results indicate that porosity, crystallinity and shift in the preferential orientation are more pronounced close to the surface than close to the bottom of the sample. Wettability upon measurement of the water contact angle, methylene blue degradation and radical formation tests under both ultraviolet and Vis irradiation demonstrate that the topmost surface renders not only a larger reactive surface area but also a better carrier transport route than the rest of the film, improving its photocatalytic activity. These results show that surface porosity of the film is dominant than the tailoring of the photocatalytic activities of N,C-codoped TiO 2 catalysts.

Delivering digital health and well-being at scale: lessons learned during the implementation of the dallas program in the United Kingdom

PubMed Central

Devlin, Alison M; McGee-Lennon, Marilyn; O’Donnell, Catherine A; Bouamrane, Matt-Mouley; Agbakoba, Ruth; O’Connor, Siobhan; Grieve, Eleanor; Finch, Tracy; Wyke, Sally; Watson, Nicholas; Browne, Susan

2016-01-01

Objective To identify implementation lessons from the United Kingdom Delivering Assisted Living Lifestyles at Scale (dallas) program—a large-scale, national technology program that aims to deliver a broad range of digital services and products to the public to promote health and well-being. Materials and Methods Prospective, longitudinal qualitative research study investigating implementation processes. Qualitative data collected includes semi-structured e-Health Implementation Toolkit–led interviews at baseline/mid-point (n = 38), quarterly evaluation, quarterly technical and barrier and solutions reports, observational logs, quarterly evaluation alignment interviews with project leads, observational data collected during meetings, and ethnographic data from dallas events (n > 200 distinct pieces of qualitative data). Data analysis was guided by Normalization Process Theory, a sociological theory that aids conceptualization of implementation issues in complex healthcare settings. Results Five key challenges were identified: 1) The challenge of establishing and maintaining large heterogeneous, multi-agency partnerships to deliver new models of healthcare; 2) The need for resilience in the face of barriers and set-backs including the backdrop of continually changing external environments; 3) The inherent tension between embracing innovative co-design and achieving delivery at pace and at scale; 4) The effects of branding and marketing issues in consumer healthcare settings; and 5) The challenge of interoperability and information governance, when commercial proprietary models are dominant. Conclusions The magnitude and ambition of the dallas program provides a unique opportunity to investigate the macro level implementation challenges faced when designing and delivering digital health and wellness services at scale. Flexibility, adaptability, and resilience are key implementation facilitators when shifting to new digitally enabled models of care. PMID:26254480

Delivering digital health and well-being at scale: lessons learned during the implementation of the dallas program in the United Kingdom.

PubMed

Devlin, Alison M; McGee-Lennon, Marilyn; O'Donnell, Catherine A; Bouamrane, Matt-Mouley; Agbakoba, Ruth; O'Connor, Siobhan; Grieve, Eleanor; Finch, Tracy; Wyke, Sally; Watson, Nicholas; Browne, Susan; Mair, Frances S

2016-01-01

To identify implementation lessons from the United Kingdom Delivering Assisted Living Lifestyles at Scale (dallas) program-a large-scale, national technology program that aims to deliver a broad range of digital services and products to the public to promote health and well-being. Prospective, longitudinal qualitative research study investigating implementation processes. Qualitative data collected includes semi-structured e-Health Implementation Toolkit-led interviews at baseline/mid-point (n = 38), quarterly evaluation, quarterly technical and barrier and solutions reports, observational logs, quarterly evaluation alignment interviews with project leads, observational data collected during meetings, and ethnographic data from dallas events (n > 200 distinct pieces of qualitative data). Data analysis was guided by Normalization Process Theory, a sociological theory that aids conceptualization of implementation issues in complex healthcare settings. Five key challenges were identified: 1) The challenge of establishing and maintaining large heterogeneous, multi-agency partnerships to deliver new models of healthcare; 2) The need for resilience in the face of barriers and set-backs including the backdrop of continually changing external environments; 3) The inherent tension between embracing innovative co-design and achieving delivery at pace and at scale; 4) The effects of branding and marketing issues in consumer healthcare settings; and 5) The challenge of interoperability and information governance, when commercial proprietary models are dominant. The magnitude and ambition of the dallas program provides a unique opportunity to investigate the macro level implementation challenges faced when designing and delivering digital health and wellness services at scale. Flexibility, adaptability, and resilience are key implementation facilitators when shifting to new digitally enabled models of care. © The Author 2015. Published by Oxford University Press on behalf of the American Medical Informatics Association.

Long-term agroecosystem research in the central Mississippi river basin: dissolved nitrogen and phosphorus transport in a high-runoff-potential watershed.

PubMed

Lerch, R N; Baffaut, C; Kitchen, N R; Sadler, E J

2015-01-01

Long-term monitoring data from agricultural watersheds are needed to determine if efforts to reduce nutrient transport from crop and pasture land have been effective. Goodwater Creek Experimental Watershed (GCEW), located in northeastern Missouri, is a high-runoff-potential watershed dominated by claypan soils. The objectives of this study were to: (i) summarize dissolved NH-N, NO-N, and PO-P flow-weighted concentrations (FWC), daily loads, and yields (unit area loads) in GCEW from 1992 to 2010; (ii) assess time trends and relationships between precipitation, land use, and fertilizer inputs and nutrient transport; and (iii) provide context to the GCEW data by comparisons with other Corn Belt watersheds. Significant declines in annual and quarterly FWCs and yields occurred for all three nutrient species during the study, and the decreases were most evident for NO-N. Substantial decreases in first- and fourth-quarter NO-N FWCs and daily loads and modest decreases in first-quarter PO-P daily loads were observed. Declines in NO-N and PO-P transport were attributed to decreased winter wheat ( L.) and increased corn ( L.) production that shifted fertilizer application from fall to spring as well as to improved management, such as increased use of incorporation. Regression models and correlation analyses indicated that precipitation, land use, and fertilizer inputs were critical factors controlling transport. Within the Mississippi River Basin, NO-N yields in GCEW were much lower than in tile-drained areas, but PO-P yields were among the highest in the basin. Overall, results demonstrated that reductions in fall-applied fertilizer and improved fertilizer management reduced N and P transport in GCEW. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

4. Northeast corner of quarters (executive officer's quarters), looking onto ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

4. Northeast corner of quarters (executive officer's quarters), looking onto Quarter R (commanding officer's quarters), looking southeast - Naval Air Station Chase Field, Texas State Highway 202, 4.8 miles east of intersection of Texas State Highway 202 & U.S. State Highway 181, Beeville, Bee County, TX

Phosphoric acid fuel cell platinum use study

NASA Technical Reports Server (NTRS)

Lundblad, H. L.

1983-01-01

The U.S. Department of Energy is promoting the private development of phosphoric acid fuel cell (PAFC) power plants for terrestrial applications. Current PAFC technology utilizes platinum as catalysts in the power electrodes. The possible repercussions that the platinum demand of PAFC power plant commercialization will have on the worldwide supply and price of platinum from the outset of commercialization to the year 2000 are investigated. The platinum demand of PAFC commercialization is estimated by developing forecasts of platinum use per unit of generating capacity and penetration of PAFC power plants into the electric generation market. The ability of the platinum supply market to meet future demands is gauged by assessing the size of platinum reserves and the capability of platinum producers to extract, refine and market sufficient quantities of these reserves. The size and timing of platinum price shifts induced by the added demand of PAFC commercialization are investigated by several analytical methods. Estimates of these price shifts are then used to calculate the subsequent effects on PAFC power plant capital costs.

Scaling Relations for Adsorption Energies on Doped Molybdenum Phosphide Surfaces

DOE PAGES

Fields, Meredith; Tsai, Charlie; Chen, Leanne D.; ...

2017-03-10

Molybdenum phosphide (MoP), a well-documented catalyst for applications ranging from hydrotreating reactions to electrochemical hydrogen evolution, has yet to be mapped from a more fundamental perspective, particularly in the context of transition-metal scaling relations. In this work, we use periodic density functional theory to extend linear scaling arguments to doped MoP surfaces and understand the behavior of the phosphorus active site. The derived linear relationships for hydrogenated C, N, and O species on a variety of doped surfaces suggest that phosphorus experiences a shift in preferred bond order depending on the degree of hydrogen substitution on the adsorbate molecule. Thismore » shift in phosphorus hybridization, dependent on the bond order of the adsorbate to the surface, can result in selective bond weakening or strengthening of chemically similar species. As a result, we discuss how this behavior deviates from transition-metal, sulfide, carbide, and nitride scaling relations, and we discuss potential applications in the context of electrochemical reduction reactions.« less

Phosphoric acid fuel cell platinum use study

NASA Astrophysics Data System (ADS)

Lundblad, H. L.

1983-05-01

The U.S. Department of Energy is promoting the private development of phosphoric acid fuel cell (PAFC) power plants for terrestrial applications. Current PAFC technology utilizes platinum as catalysts in the power electrodes. The possible repercussions that the platinum demand of PAFC power plant commercialization will have on the worldwide supply and price of platinum from the outset of commercialization to the year 2000 are investigated. The platinum demand of PAFC commercialization is estimated by developing forecasts of platinum use per unit of generating capacity and penetration of PAFC power plants into the electric generation market. The ability of the platinum supply market to meet future demands is gauged by assessing the size of platinum reserves and the capability of platinum producers to extract, refine and market sufficient quantities of these reserves. The size and timing of platinum price shifts induced by the added demand of PAFC commercialization are investigated by several analytical methods. Estimates of these price shifts are then used to calculate the subsequent effects on PAFC power plant capital costs.

Variation of the energy release rate as a crack approaches and passes through an elastic inclusion

NASA Astrophysics Data System (ADS)

Li, Rongshun; Chudnovsky, A.

1993-02-01

The variation of the energy release rate (ERP) at the tip of a crack penetrating an elastic inclusion is analyzed using an approach involving modeling the random array of microcracks or other defects by an elastic inclusion with effective elastic properties. Computations are carried out using a finite element procedure. The eight-noded isoparametric serendipity element with the shift of the midpoint to the quarter-point is used to simulate the singularity at the crack tip, and the crack growth is accommodated by implementing a mesh regeneration technique. The ERP values were calculated for various crack tip positions which simulate the process of the crack approaching and penetrating the inclusion.

Variation of the energy release rate as a crack approaches and passes through an elastic inclusion

NASA Technical Reports Server (NTRS)

Li, Rongshun; Chudnovsky, A.

1993-01-01

The variation of the energy release rate (ERP) at the tip of a crack penetrating an elastic inclusion is analyzed using an approach involving modeling the random array of microcracks or other defects by an elastic inclusion with effective elastic properties. Computations are carried out using a finite element procedure. The eight-noded isoparametric serendipity element with the shift of the midpoint to the quarter-point is used to simulate the singularity at the crack tip, and the crack growth is accommodated by implementing a mesh regeneration technique. The ERP values were calculated for various crack tip positions which simulate the process of the crack approaching and penetrating the inclusion.

Use of task-shifting to rapidly scale-up HIV treatment services: experiences from Lusaka, Zambia

PubMed Central

Morris, Mary B; Chapula, Bushimbwa Tambatamba; Chi, Benjamin H; Mwango, Albert; Chi, Harmony F; Mwanza, Joyce; Manda, Handson; Bolton, Carolyn; Pankratz, Debra S; Stringer, Jeffrey SA; Reid, Stewart E

2009-01-01

The World Health Organization advocates task-shifting, the process of delegating clinical care functions from more specialized to less specialized health workers, as a strategy to achieve the United Nations Millennium Development Goals. However, there is a dearth of literature describing task shifting in sub-Saharan Africa, where services for antiretroviral therapy (ART) have scaled up rapidly in the face of generalized human resource crises. As part of ART services expansion in Lusaka, Zambia, we implemented a comprehensive task-shifting program among existing health providers and community-based workers. Training begins with didactic sessions targeting specialized skill sets. This is followed by an intensive period of practical mentorship, where providers are paired with trainers before working independently. We provide on-going quality assessment using key indicators of clinical care quality at each site. Program performance is reviewed with clinic-based staff quarterly. When problems are identified, clinic staff members design and implement specific interventions to address targeted areas. From 2005 to 2007, we trained 516 health providers in adult HIV treatment; 270 in pediatric HIV treatment; 341 in adherence counseling; 91 in a specialty nurse "triage" course, and 93 in an intensive clinical mentorship program. On-going quality assessment demonstrated improvement across clinical care quality indicators, despite rapidly growing patient volumes. Our task-shifting strategy was designed to address current health care worker needs and to sustain ART scale-up activities. While this approach has been successful, long-term solutions to the human resource crisis are also urgently needed to expand the number of providers and to slow staff migration out of the region. PMID:19134202

Shifts in an invasive rodent community favoring black rats (Rattus rattus) following restoration of native forest

USGS Publications Warehouse

Shiels, Aaron B.; Medeiros, Arthur C.; von Allmen, Erica I.

2017-01-01

One potential, unintended ecological consequence accompanying forest restoration is a shift in invasive animal populations, potentially impacting conservation targets. Eighteen years after initial restoration (ungulate exclusion, invasive plant control, and out planting native species) at a 4 ha site on Maui, Hawai'i, we compared invasive rodent communities in a restored native dry forest and adjacent non-native grassland. Quarterly for 1 year, we trapped rodents on three replicate transects (107 rodent traps) in each habitat type for three consecutive nights. While repeated trapping may have reduced the rat (Black rat, Rattus rattus) population in the forest, it did not appear to reduce the mouse (House mouse, Mus musculus) population in the grassland. In unrestored grassland, mouse captures outnumbered rat captures 220:1, with mice averaging 54.9 indiv./night versus rats averaging 0.25 indiv./night. In contrast, in restored native forest, rat captures outnumbered mouse captures by nearly 5:1, averaging 9.0 indiv./night versus 1.9 indiv./night for mice. Therefore, relatively recent native forest restoration increased Black rat abundance and also increased their total biomass in the restored ecosystem 36-fold while reducing House mouse biomass 35-fold. Such a community shift is worrisome because Black rats pose a much greater threat than do mice to native birds and plants, perhaps especially to large-seeded tree species. Land managers should be aware that forest restoration (i.e. converting grassland to native forest) can invoke shifts in invasive rodent populations, potentially favoring Black rats. Without intervention, this shift may pose risks for intended conservation targets and modify future forest restoration trajectories.

12 CFR 1777.10 - Developments prompting supervisory response.

Code of Federal Regulations, 2011 CFR

2011-01-01

...) An Enterprise's publicly reported net income for the most recent calendar quarter is less than one-half of its average quarterly net income for any four-quarter period during the prior eight quarters... than one-half of its average NIM for any four-quarter period during the prior eight quarters; (d) For...

Synthesis and characterization of C-doped TiO2 thin films for visible-light-induced photocatalytic degradation of methyl orange

NASA Astrophysics Data System (ADS)

Hassan, Mohamed Elfatih; Cong, Longchao; Liu, Guanglong; Zhu, Duanwei; Cai, Jianbo

2014-03-01

C-TiO2 thin films were synthesized by a modified sol-gel route based on the self-assembly technique exploiting Tween80 (T80) as a pore directing agent and carbon source. The effect of calcination time on the photocatalytic activity of C-doped TiO2 catalyst was studied. The samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transforms infrared (FTIR), UV-vis diffuse reflectance spectroscopy, and photoluminescence spectra (PL). The XRD results showed that C-TiO2 sample calcined at 400 °C for various times exhibited anatase phase and no other crystal phase was identified. C-TiO2 exhibited a shift in an absorption edge of samples in the visible region than that of conventional or reference TiO2. The XPS results showed an existence of C in the TiO2 catalysts and C might be existed as Csbnd Osbnd Ti group. Moreover, the C-TiO2 thin film calcined at 400 °C for 30 min showed the lowest PL intensity due to a decrease in the recombination rate of photogenerated electrons and holes under UV light irradiation. Also the photocatalytic activity of synthesized catalyst was evaluated by decomposition of methyl orange (MO) under visible light irradiation. The results showed that the optimum preparations of C-TiO2 thin films were found to be under calcination temperature of 400, calcination time of 30 min, and with preparation 9 layers film.

Apparatus and method for simultaneous recovery of hydrogen from water and from hydrocarbons

DOEpatents

Willms, R. Scott; Birdsell, Stephen A.

2000-01-01

Apparatus and method for simultaneous recovery of hydrogen from water and from hydrocarbon feed material. The feed material is caused to flow over a heated catalyst which fosters the water-gas shift reaction (H.sub.2 O+COH.sub.2 +CO.sub.2) and the methane steam reforming reaction (CH.sub.4 +H.sub.2 O3 H.sub.2 +CO). Both of these reactions proceed only to partial completion. However, by use of a Pd/Ag membrane which is exclusively permeable to hydrogen isotopes in the vicinity of the above reactions and by maintaining a vacuum on the permeate side of the membrane, product hydrogen isotopes are removed and the reactions are caused to proceed further toward completion. A two-stage palladium membrane reactor was tested with a feed composition of 28% CQ.sub.4, 35% Q.sub.2 O (where Q=H, D, or T), and 31% Ar in 31 hours of continuous operation during which 4.5 g of tritium were processed. Decontamination factors were found to increase with decreasing inlet rate. The first stage was observed to have a decontamination factor of approximately 200, while the second stage had a decontamination factor of 2.9.times.10.sup.6. The overall decontamination factor was 5.8.times.10.sup.8. When a Pt/.alpha.-Al.sub.2 O.sub.3 catalyst is employed, decoking could be performed without catalyst degradation. However, by adjusting the carbon to oxygen ratio of the feed material with the addition of oxygen, coking could be altogether avoided.

Characteristics of Pt-K/MgAl2O4 lean NOx trap catalysts

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

Kim, Do Heui; Mudiyanselage, Kumudu K.; Szanyi, Janos

2012-04-30

We report the various characteristics of Pt-K/MgAl{sub 2}O{sub 4} lean NOx trap (LNT) catalysts including the effect of K loading on nitrate formation/decomposition, NOx storage activity and durability. Upon the adsorption of NO{sub 2} on K/MgAl{sub 2}O{sub 4} samples, potassium nitrates formed on Mg-related sites in MgAl{sub 2}O{sub 4} support are observed, in addition to the typical two potassium nitrates (ionic and bidentate) formed also on Al{sub 2}O{sub 3} supported sample. Based on NO{sub 2} TPD and FTIR results, the Mg-bound KNO{sub 3} thermally decompose at higher temperature than Al-bound KNO{sub 3}, implying its superior thermal stability. At a potassiummore » loading of 5wt%, the temperature of maximum NOx uptake (T{sub max}) is 300 C. Increasing the potassium loading from 5wt% to 10 wt%, the T{sub max} gradually shifted from 300 C to 450 C, indicating the dependence of T{sub max} on the potassium loading. However, increase in potassium loading above 10 wt% only gives rise to the reduction in the overall NOx storage capacity. This work also underlines the obstacles these materials have prior to their practical application (e.g., durability and sulfur poisoning/ removal). This work provides fundamental understanding of Pt-K/MgAl{sub 2}O{sub 4}-based lean NOx trap catalysts, which could be good candidates for high temperature LNT applications.« less

Enhanced methanol electro-oxidation reaction on Pt-CoOx/MWCNTs hybrid electro-catalyst

NASA Astrophysics Data System (ADS)

Nouralishahi, Amideddin; Rashidi, Ali Morad; Mortazavi, Yadollah; Khodadadi, Abbas Ali; Choolaei, Mohammadmehdi

2015-04-01

The electro-catalytic behavior of Pt-CoOx/MWCNTs in methanol electro-oxidation reaction (MOR) is investigated and compared to that of Pt/MWCNTs. The electro-catalysts were synthesized by an impregnation method using NaBH4 as the reducing agent. The morphological and physical characteristics of samples are examined by XRD, TEM, ICP and EDS techniques. In the presence of CoOx, Pt nanoparticles were highly distributed on the support with an average particle size of 2 nm, an obvious decrease from 5.1 nm for Pt/MWCNTs. Cyclic voltammetry, CO-stripping, Chronoamperometry, and electrochemical impedance spectroscopy (EIS) measurements are used to study the electrochemical behavior of the electro-catalysts. The results revealed a considerable enhancement in the oxidation kinetics of COads on Pt active sites by the participation of CoOx. Compared to Pt/MWCNTs, Pt-CoOx/MWCNTs sample has a larger electrochemical active surface area (ECSA) and higher electro-catalytic activity and stability toward methanol electro-oxidation. According to the results of cyclic voltammetry, the forward anodic peak current density enhances more than 89% at the optimum atomic ratio of Pt:Co = 2:1. Furthermore, inclusion of cobalt oxide species causes the onset potential of methanol electro-oxidation reaction to shift 84 mV to negative values compared to that on Pt/MWCNTs. Based on EIS data, dehydrogenation of methanol is the rate-determining step of MOR on both Pt/MWCNTs and Pt-CoOx/MWCNTs, at small overpotentials. However, at higher overpotentials, the oxidation of adsorbed oxygen-containing groups controls the total rate of MOR process.

Integrative Pericyclic Cascade: An Atom Economic, Multi C-C Bond-Forming Strategy for the Construction of Molecular Complexity.

PubMed

Tejedor, David; Delgado-Hernández, Samuel; Peyrac, Jesús; González-Platas, Javier; García-Tellado, Fernando

2017-07-26

An all-pericyclic manifold is developed for the construction of topologically diverse, structurally complex and natural product-like polycyclic chemotypes. The manifold uses readily accessible tertiary propargyl vinyl ethers as substrates and imidazole as a catalyst to form up to two new rings, three new C-C bonds, six stereogenic centers and one transannular oxo-bridge. The manifold is efficient, scalable and instrumentally simple to perform and entails a propargyl Claisen rearrangement-[1,3]H shift, an oxa-6π-electrocyclization, and an intramolecular Diels-Alder reaction. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photonic bandgap narrowing in conical hollow core Bragg fibers

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

Ozturk, Fahri Emre; Yildirim, Adem; Kanik, Mehmet

2014-08-18

We report the photonic bandgap engineering of Bragg fibers by controlling the thickness profile of the fiber during the thermal drawing. Conical hollow core Bragg fibers were produced by thermal drawing under a rapidly alternating load, which was applied by introducing steep changes to the fiber drawing speed. In conventional cylindrical Bragg fibers, light is guided by omnidirectional reflections from interior dielectric mirrors with a single quarter wave stack period. In conical fibers, the diameter reduction introduced a gradient of the quarter wave stack period along the length of the fiber. Therefore, the light guided within the fiber encountered slightlymore » smaller dielectric layer thicknesses at each reflection, resulting in a progressive blueshift of the reflectance spectrum. As the reflectance spectrum shifts, longer wavelengths of the initial bandgap cease to be omnidirectionally reflected and exit through the cladding, which narrows the photonic bandgap. A narrow transmission bandwidth is particularly desirable in hollow waveguide mid-infrared sensing schemes, where broadband light is coupled to the fiber and the analyte vapor is introduced into the hollow core to measure infrared absorption. We carried out sensing simulations using the absorption spectrum of isopropyl alcohol vapor to demonstrate the importance of narrow bandgap fibers in chemical sensing applications.« less

3. Southwest side of quarters R (commanding officer's quarters), looking ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

3. Southwest side of quarters R (commanding officer's quarters), looking east - Naval Air Station Chase Field, Quarters R, Essex Street, .43 mile South-Southeast of intersection of Texas State Highway 202 & Independence Street, Beeville, Bee County, TX

6. Interior of quarters (executive officer's quarters), living room, looking ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

6. Interior of quarters (executive officer's quarters), living room, looking west - Naval Air Station Chase Field, Quarters S, Essex Street, .45 mile South-Southeast of intersection of Texas State Highway 202 & Independence Street, Beeville, Bee County, TX

1. North side of quarters (executive officer's quarters), looking southeast ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

1. North side of quarters (executive officer's quarters), looking southeast - Naval Air Station Chase Field, Quarters S, Essex Street, .45 mile South-Southeast of intersection of Texas State Highway 202 & Independence Street, Beeville, Bee County, TX

5. East side of quarters (executive officer's quarters), looking west ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

5. East side of quarters (executive officer's quarters), looking west - Naval Air Station Chase Field, Quarters S, Essex Street, .45 mile South-Southeast of intersection of Texas State Highway 202 & Independence Street, Beeville, Bee County, TX

1. Northeast side of Quarters R (commanding officer's quarters), looking ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

1. Northeast side of Quarters R (commanding officer's quarters), looking west - Naval Air Station Chase Field, Quarters R, Essex Street, .43 mile South-Southeast of intersection of Texas State Highway 202 & Independence Street, Beeville, Bee County, TX

2. West side of quarters (executive officer's quarters), looking east ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

2. West side of quarters (executive officer's quarters), looking east - Naval Air Station Chase Field, Quarters S, Essex Street, .45 mile South-Southeast of intersection of Texas State Highway 202 & Independence Street, Beeville, Bee County, TX

2. Southeast side of Quarters R (commanding officer's quarters), looking ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

2. Southeast side of Quarters R (commanding officer's quarters), looking northwest - Naval Air Station Chase Field, Quarters R, Essex Street, .43 mile South-Southeast of intersection of Texas State Highway 202 & Independence Street, Beeville, Bee County, TX

4. Northwest side of Quarters R (commanding officer's quarters), looking ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

4. Northwest side of Quarters R (commanding officer's quarters), looking southeast - Naval Air Station Chase Field, Quarters R, Essex Street, .43 mile South-Southeast of intersection of Texas State Highway 202 & Independence Street, Beeville, Bee County, TX

4. South side of quarters (executive officer's quarters), looking north ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

4. South side of quarters (executive officer's quarters), looking north - Naval Air Station Chase Field, Quarters S, Essex Street, .45 mile South-Southeast of intersection of Texas State Highway 202 & Independence Street, Beeville, Bee County, TX

3. Southwest side of quarters (executive officer's quarters), looking northeast ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

3. Southwest side of quarters (executive officer's quarters), looking northeast - Naval Air Station Chase Field, Quarters S, Essex Street, .45 mile South-Southeast of intersection of Texas State Highway 202 & Independence Street, Beeville, Bee County, TX

Decadal Variability of Temperature and Salinity in the Northwest Atlantic Ocean

NASA Astrophysics Data System (ADS)

Mishonov, A. V.; Seidov, D.; Reagan, J. R.; Boyer, T.; Parsons, A. R.

2017-12-01

There are only a few regions in the World Ocean where the density of observations collected over the past 60 years is sufficient for reliable data mapping with spatial resolutions finer than one-degree. The Northwest Atlantic basin is one such regions where a spatial resolution of gridded temperature and salinity fields, comparable to those generated by eddy-resolving numerical models of ocean circulation, has recently becomes available. Using the new high-resolution Northwest Atlantic Regional Climatology, built on quarter-degree and one-tenth-degree resolution fields, we analyzed decadal variability and trends of temperature and salinity over 60 years in the Northwest Atlantic, and two 30-year ocean climates of 1955-1984 and 1985-2012 to evaluate the oceanic climate shift in this region. The 30-year climate shift is demonstrated using an innovative 3-D visualization of temperature and salinity. Spatial and temporal variability of heat accumulation found in previous research of the entire North Atlantic Ocean persists in the Northwest Atlantic Ocean. Salinity changes between two 30-year climates were also computed and are discussed.

Shearing interference microscope for step-height measurements.

PubMed

Trịnh, Hưng-Xuân; Lin, Shyh-Tsong; Chen, Liang-Chia; Yeh, Sheng-Lih; Chen, Chin-Sheng; Hoang, Hong-Hai

2017-05-01

A shearing interference microscope using a Savart prism as the shear plate is proposed for inspecting step-heights. Where the light beam propagates through the Savart prism and microscopic system to illuminate the sample, it then turns back to re-pass through the Savart prism and microscopic system to generate a shearing interference pattern on the camera. Two measurement modes, phase-shifting and phase-scanning, can be utilized to determine the depths of the step-heights on the sample. The first mode, which employs a narrowband source, is based on the five-step phase-shifting algorithm and has a measurement range of a quarter-wavelength. The second mode, which adopts a broadband source, is based on peak-intensity identification technology and has a measurement range up to a few micrometres. This paper is to introduce the configuration and measurement theory of this microscope, perform a setup used to implement it, and present the experimental results from the uses of the setup. The results not only verify the validity but also confirm the high measurement repeatability of the proposed microscope. © 2017 The Authors Journal of Microscopy © 2017 Royal Microscopical Society.

Multi-level diffractive optics for single laser exposure fabrication of telecom-band diamond-like 3-dimensional photonic crystals.

PubMed

Chanda, Debashis; Abolghasemi, Ladan E; Haque, Moez; Ng, Mi Li; Herman, Peter R

2008-09-29

We present a novel multi-level diffractive optical element for diffractive optic near-field lithography based fabrication of large-area diamond-like photonic crystal structure in a single laser exposure step. A multi-level single-surface phase element was laser fabricated on a thin polymer film by two-photon polymerization. A quarter-period phase shift was designed into the phase elements to generate a 3D periodic intensity distribution of double basis diamond-like structure. Finite difference time domain calculation of near-field diffraction patterns and associated isointensity surfaces are corroborated by definitive demonstration of a diamond-like woodpile structure formed inside thick photoresist. A large number of layers provided a strong stopband in the telecom band that matched predictions of numerical band calculation. SEM and spectral observations indicate good structural uniformity over large exposure area that promises 3D photonic crystal devices with high optical quality for a wide range of motif shapes and symmetries. Optical sensing is demonstrated by spectral shifts of the Gamma-Zeta stopband under liquid emersion.

Conformational Change in the Active Site of Streptococcal Unsaturated Glucuronyl Hydrolase Through Site-Directed Mutagenesis at Asp-115.

PubMed

Nakamichi, Yusuke; Oiki, Sayoko; Mikami, Bunzo; Murata, Kousaku; Hashimoto, Wataru

2016-08-01

Bacterial unsaturated glucuronyl hydrolase (UGL) degrades unsaturated disaccharides generated from mammalian extracellular matrices, glycosaminoglycans, by polysaccharide lyases. Two Asp residues, Asp-115 and Asp-175 of Streptococcus agalactiae UGL (SagUGL), are completely conserved in other bacterial UGLs, one of which (Asp-175 of SagUGL) acts as a general acid and base catalyst. The other Asp (Asp-115 of SagUGL) also affects the enzyme activity, although its role in the enzyme reaction has not been well understood. Here, we show substitution of Asp-115 in SagUGL with Asn caused a conformational change in the active site. Tertiary structures of SagUGL mutants D115N and D115N/K370S with negligible enzyme activity were determined at 2.00 and 1.79 Å resolution, respectively, by X-ray crystallography. The side chain of Asn-115 is drastically shifted in both mutants owing to the interaction with several residues, including Asp-175, by formation of hydrogen bonds. This interaction between Asn-115 and Asp-175 probably prevents the mutants from triggering the enzyme reaction using Asp-175 as an acid catalyst.

Defect engineering of mesoporous nickel ferrite and its application for highly enhanced water oxidation catalysis

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

Yue, Qiudi; Liu, Cunming; Wan, Yangyang

Spinel nickel ferrite (NiFe2O4) emerges as a promising low-cost catalyst for water splitting but it usually shows low catalytic activity because of its limited number of active sites and poor conductivity. For the first time, herein we have successfully overcome its weaknesses using defect engineering approach by creating oxygen vacancies in NiFe2O4. The existence of oxygen vacancy not only shifts up the d-band center, strengthens the adsorption of H2O, and thus provides more active catalytic sites, but also tunes the electron configuration and creates massive number of defective donor states in the band gap to facilitate charge transfer processes. Themore » optimal defective catalyst showed significantly enhanced catalytic OER performance with an OER overpotential as low as 0.35 V at 10 mA cm-2 and a Tafel slope of only ~40 mV dec-1. Moreover, the impressive specific mass and area current density of 17.5 A g-1 and 0.106 A m-2 at 1.58 V vs. RHE have been achieved, which are ~23 and ~36 times higher than that of defect-free counterpart, respectively.« less

Mechanism of spontaneous polarization transfer in high-field SABRE experiments

NASA Astrophysics Data System (ADS)

Knecht, Stephan; Kiryutin, Alexey S.; Yurkovskaya, Alexandra V.; Ivanov, Konstantin L.

2018-02-01

We propose an explanation of the previously reported SABRE (Signal Amplification By Reversible Exchange) effect at high magnetic fields, observed in the absence of RF-excitation and relying only on "spontaneous" polarization transfer from parahydrogen (pH2, the H2 molecule in its nuclear singlet spin state) to a SABRE substrate. We propose a detailed mechanism for spontaneous polarization transfer and show that it is comprised of three steps: (i) Generation of the anti-phase Î1zÎ2z spin order of catalyst-bound H2; (ii) spin order conversion Î1zÎ2z → (Î1z +Î2z) due to cross-correlated relaxation, leading to net polarization of H2; (iii) polarization transfer to the SABRE substrate, occurring due to NOE. Formation of anti-phase polarization is due to singlet-to-T0 mixing in the catalyst-bound form of H2, while cross-correlated relaxation originates from fluctuations of dipole-dipole interactions and chemical shift anisotropy. The proposed mechanism is supported by a theoretical treatment, magnetic field-dependent studies and high-field NMR measurements with both pH2 and thermally polarized H2.

Mechanism of spontaneous polarization transfer in high-field SABRE experiments.

PubMed

Knecht, Stephan; Kiryutin, Alexey S; Yurkovskaya, Alexandra V; Ivanov, Konstantin L

2018-02-01

We propose an explanation of the previously reported SABRE (Signal Amplification By Reversible Exchange) effect at high magnetic fields, observed in the absence of RF-excitation and relying only on "spontaneous" polarization transfer from parahydrogen (pH 2 , the H 2 molecule in its nuclear singlet spin state) to a SABRE substrate. We propose a detailed mechanism for spontaneous polarization transfer and show that it is comprised of three steps: (i) Generation of the anti-phase Î 1z Î 2z spin order of catalyst-bound H 2 ; (ii) spin order conversion Î 1z Î 2z →(Î 1z +Î 2z ) due to cross-correlated relaxation, leading to net polarization of H 2 ; (iii) polarization transfer to the SABRE substrate, occurring due to NOE. Formation of anti-phase polarization is due to singlet-to-T 0 mixing in the catalyst-bound form of H 2 , while cross-correlated relaxation originates from fluctuations of dipole-dipole interactions and chemical shift anisotropy. The proposed mechanism is supported by a theoretical treatment, magnetic field-dependent studies and high-field NMR measurements with both pH 2 and thermally polarized H 2 . Copyright © 2017 Elsevier Inc. All rights reserved.

Catalytic dehydration of biomass derived 1-propanol to propene over M-ZSM-5 (M = H, V, Cu, or Zn)

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

Lepore, Andrew W.; Li, Zhenglong; Davison, Brian H.

Here, the impetus to explore biomass derived chemicals arises from a desire to enable renewable and sustainable commodity chemicals. To this end, we report catalytic production of propene, a building-block molecule, from 1-propanol. We found that zeolite catalysts are quite versatile and can produce propene at or below 230 C with high selectivity. Increasing the reaction temperature above 230 C shifted product selectivity towards C4+ hydrocarbons. Cu-ZSM-5 was found to exhibit a broader temperature window for high propene selectivity and could function at higher 1-propanol space velocities than H-ZSM-5. A series of experiments with 1-propan(ol-D) showed deuterium incorporation in themore » hydrocarbon product stream including propene suggesting that hydrocarbon pool type pathway might be operational concurrent with dehydration to produce C4+ hydrocarbons. Diffuse reflectance infra-red spectroscopy of 1-propanol and 1-propan(ol-D) over Cu-ZSM-5 in combination with deuterium labeling experiments suggest that deuterium incorporation occurs in two steps. Incorporation of deuterium occurs post dehydration via exchange with the partially deuterated catalyst surface.« less

Role of basic and acidic centers of MgO and modified MgO in catalytic transfer hydrogenation of ketones studied by infrared spectroscopy

NASA Astrophysics Data System (ADS)

Szöllösi, György; Bartók, Mihály

1999-05-01

In this study our aim was to identify the active sites and the surface species responsible for deactivation of MgO during catalytic transfer hydrogenations (CTH) of ketones using alcohols as hydrogen donors. Our previous studies showed that deactivation of MgO could be prevented by previous treatment with chloromethanes. Therefore the surface species formed during the reaction were studied before and after treatment with chloroform or chloroform- d by in situ infrared spectroscopy (IR). As a result, it was concluded that the reaction requires the presence of surface basic and acidic centers. The presence of Lewis acid centers was not necessary, the reaction could proceed on weakly acidic surface Brönsted sites, as the alterations in intensity and position of the ν(OH) bands indicated. Modification with chloroform resulted also in the generation of surface OH groups with a proper acidity for the reaction. The shift in carbonyl vibrations led us to the conclusion that Lewis acid and base centers were responsible for the catalyst poisoning, so covering these acid sites by Cl - led to a stable catalyst.

Catalytic dehydration of biomass derived 1-propanol to propene over M-ZSM-5 (M = H, V, Cu, or Zn)

DOE PAGES

Lepore, Andrew W.; Li, Zhenglong; Davison, Brian H.; ...

2017-04-03

Here, the impetus to explore biomass derived chemicals arises from a desire to enable renewable and sustainable commodity chemicals. To this end, we report catalytic production of propene, a building-block molecule, from 1-propanol. We found that zeolite catalysts are quite versatile and can produce propene at or below 230 C with high selectivity. Increasing the reaction temperature above 230 C shifted product selectivity towards C4+ hydrocarbons. Cu-ZSM-5 was found to exhibit a broader temperature window for high propene selectivity and could function at higher 1-propanol space velocities than H-ZSM-5. A series of experiments with 1-propan(ol-D) showed deuterium incorporation in themore » hydrocarbon product stream including propene suggesting that hydrocarbon pool type pathway might be operational concurrent with dehydration to produce C4+ hydrocarbons. Diffuse reflectance infra-red spectroscopy of 1-propanol and 1-propan(ol-D) over Cu-ZSM-5 in combination with deuterium labeling experiments suggest that deuterium incorporation occurs in two steps. Incorporation of deuterium occurs post dehydration via exchange with the partially deuterated catalyst surface.« less

In situ {sup 13}C MAS NMR study of n-hexane conversion on Pt and Pd supported on basic materials

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

Ivanova, I.I.; Pasau-Claerbout, A.; Seivert, M.

n-Hexane conversion was studied in situ on Pt and Pd supported on aluminum-stabilized magnesium oxide and Pt on Zeolite KL catalysts (Pt/Mg(Al)O, Pd/Mg(Al)O and Pt/KL) by means of {sup 13}C MAS NMR spectroscopy. n-Hexane 1-{sup 13}C was used as a labelled reactant. Forty NMR lines corresponding to 14 different products were resolved and identified. The NMR line assignments were confirmed by adsorption of model compounds. The NMR results were further quantified and compared with continuous flow microreactor tests. Four parallel reaction pathways were identified under flow conditions: isomerization, cracking, dehydrocyclization, and dehydrogenation. Aromatization occurs via two reaction routes: (1) n-hexanemore » dehydrogenation towards hexadienes and hexatrienes, followed by dehydrogenation of a cyclic intermediate. The former reaction pathway is prevented under NMR batch conditions. High pressures induced in the NMR cells at high reaction temperatures (573, 653 K) shift the reaction equilibrium towards hydrogenation. NMR experiments showed that on Pt catalysts aromatization occurs via a cyclohexane intermediate, whereas on Pd it takes place via methylcyclopentane ring enlargement. 54 refs., 15 figs., 3 tabs.« less

A theoretical study on the mechanism of hydrogen evolution on non-precious partially oxidized nickel-based heterostructures for fuel cells.

PubMed

Pan, Xinju; Zhou, Gang

2018-03-28

It is desirable, yet challenging, to utilize non-precious metals instead of noble-metals as efficient catalysts in the renewable energy manufacturing industry. Using first principles calculations, we study the structural characteristics of partially oxidized nickel-based nanoheterostructures (NiO/Ni NHSs), and the interfacial effects on hydrogen evolution. The origin of the enhanced hydrogen evolution performance is discussed at the microscopic level. This study identifies two types of active sites of the exposed Ni surface available for the hydrogen evolution reaction (HER). One is the hcp-hollow sites near the perimeter boundary that exhibit a more excellent HER performance than platinum (Pt), and the other the second nearest neighbor fcc-hollow sites away from the boundary that exhibit a similar performance to Pt. The interfacial effects result from the competitive charge transfer between NiO and Ni surfaces in NHSs, and enhance the reactivity of NiO/Ni NHSs by shifting the d-states of surface atoms down in energy. The illumination of the mechanism would be helpful for the design of more efficient and cheap transition metal-based catalysts.

5. Interior of Quarters R (commanding officer's quarters), living room, ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

5. Interior of Quarters R (commanding officer's quarters), living room, looking northwest - Naval Air Station Chase Field, Quarters R, Essex Street, .43 mile South-Southeast of intersection of Texas State Highway 202 & Independence Street, Beeville, Bee County, TX

33 CFR 117.261 - Atlantic Intracoastal Waterway from St. Marys River to Key Largo.

Code of Federal Regulations, 2012 CFR

2012-07-01

... draw shall open on the quarter and three-quarter hour. (u) Flagler Memorial (SR A1A) bridge, mile 1020... (SR 700/80) bridge, mile 1024.7 at Palm Beach. The draw shall open on the quarter and three-quarter... open on the quarter and three-quarter-hour. (z-2) Linton Boulevard bridge, mile 1041.1, at Delray Beach...

33 CFR 117.261 - Atlantic Intracoastal Waterway from St. Marys River to Key Largo.

Code of Federal Regulations, 2011 CFR

2011-07-01

... draw shall open on the quarter and three-quarter hour. (u) Flagler Memorial (SR A1A) bridge, mile 1020... (SR 700/80) bridge, mile 1024.7 at Palm Beach. The draw shall open on the quarter and three-quarter... open on the quarter and three-quarter-hour. (z-2) Linton Boulevard bridge, mile 1041.1, at Delray Beach...

33 CFR 117.261 - Atlantic Intracoastal Waterway from St. Marys River to Key Largo.

Code of Federal Regulations, 2013 CFR

2013-07-01

... draw shall open on the quarter and three-quarter hour. (u) Flagler Memorial (SR A1A) bridge, mile 1020... (SR 700/80) bridge, mile 1024.7 at Palm Beach. The draw shall open on the quarter and three-quarter... open on the quarter and three-quarter-hour. (z-2) Linton Boulevard bridge, mile 1041.1, at Delray Beach...

[Development of cell content and shedding of Prototheca spp. in milk from infected udder quarters of cows].

PubMed

Tenhagen, B A; Hille, A; Schmidt, A; Heuwieser, W

2005-02-01

It was the objective of this study to analyse shedding patterns and somatic cell counts in cows and quarters infected with Prototheca spp. and to evaluate two approaches to identify infected animals by somatic cell count (SCC) or by bacteriological analysis of pooled milk samples. Five lactating dairy cows, chronically infected with Prototheca spp. in at least one quarter were studied over 11 weeks to 13 months. Quarter milk samples and a pooled milk sample from 4 quarters were collected aseptically from all quarters of the cows on a weekly basis. Culture results of quarter milk and pooled samples were compared using cross tabulation. SCC of quarter milk samples and of pooled samples were related to the probability of detection in the infected quarters and cows, respectively. Shedding of Prototheca spp. was continuous in 2 of 8 quarters. In the other quarters negative samples were obtained sporadically or over a longer period (1 quarter). Overall, Prototheca spp. were isolated from 83.6% of quarter milk samples and 77.0% of pooled milk samples of infected quarters and cows. Somatic cell counts were higher in those samples from infected quarters that contained the algae than in negative samples (p < 0.0001). The same applied for composite samples from infected cows. Positive samples had higher SCC than negative samples. However, Prototheca spp. were also isolated from quarter milk and pooled samples with physiological SCC (i.e. < 10(5)/ml). Infected quarters that were dried off did not develop acute mastitis. However, drying off had no effect on the infection, i.e. samples collected at calving or 8 weeks after dry off still contained Prototheca spp. Results indicate that pre-selection of cows to be sampled for Prototheca spp. by SCC and the use of composite samples are probably inadequate in attempts to eradicate the disease. However, due to intermittent shedding of the algae in some cows, single herd sampling using quarter milk samples probably also fails to detect all infected cases. Therefore, continuous monitoring of problem cows with clinical mastitis or increased SCC in herds during eradication programs is recommended.

Magnetic susceptibility as a direct measure of oxidation state in LiFePO4 batteries and cyclic water gas shift reactors.

PubMed

Kadyk, Thomas; Eikerling, Michael

2015-08-14

The possibility of correlating the magnetic susceptibility to the oxidation state of the porous active mass in a chemical or electrochemical reactor was analyzed. The magnetic permeability was calculated using a hierarchical model of the reactor. This model was applied to two practical examples: LiFePO4 batteries, in which the oxidation state corresponds with the state-of-charge, and cyclic water gas shift reactors, in which the oxidation state corresponds to the depletion of the catalyst. In LiFePO4 batteries phase separation of the lithiated and delithiated phases in the LiFePO4 particles in the positive electrode gives rise to a hysteresis effect, i.e. the magnetic permeability depends on the history of the electrode. During fast charge or discharge, non-uniform lithium distributionin the electrode decreases the hysteresis effect. However, the overall sensitivity of the magnetic response to the state-of-charge lies in the range of 0.03%, which makes practical measurement challenging. In cyclic water gas shift reactors, the sensitivity is 4 orders of magnitude higher and without phase separation, no hysteresis occurs. This shows that the method is suitable for such reactors, in which large changes of the magnetic permeability of the active material occurs.

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.

12 CFR 1777.10 - Developments prompting supervisory response.

Code of Federal Regulations, 2010 CFR

2010-01-01

... less than the national HPI four quarters previously, or for any Census Division or Divisions in which... more than five percent less than the HPI for that Division or Divisions four quarters previously; (b...-half of its average quarterly net income for any four-quarter period during the prior eight quarters...

18 CFR 35.10b - Electric Quarterly Reports.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 18 Conservation of Power and Water Resources 1 2010-04-01 2010-04-01 false Electric Quarterly... Application § 35.10b Electric Quarterly Reports. Each public utility shall file an updated Electric Quarterly..., file by January 31. Electric Quarterly Reports must be prepared in conformance with the Commission's...

18 CFR 35.10b - Electric Quarterly Reports.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 18 Conservation of Power and Water Resources 1 2011-04-01 2011-04-01 false Electric Quarterly... Application § 35.10b Electric Quarterly Reports. Each public utility shall file an updated Electric Quarterly..., file by January 31. Electric Quarterly Reports must be prepared in conformance with the Commission's...

18 CFR 35.10b - Electric Quarterly Reports.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 18 Conservation of Power and Water Resources 1 2012-04-01 2012-04-01 false Electric Quarterly... Application § 35.10b Electric Quarterly Reports. Each public utility shall file an updated Electric Quarterly..., file by January 31. Electric Quarterly Reports must be prepared in conformance with the Commission's...

Synthesis and Characterization of Mixed-Conducting Corrosion Resistant Oxide Supports

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

Ramani, Vijay K.

An extensive search and evaluation of electrochemically stable catalyst supports (including metal oxides like RuO2-SiO2, RuO2-TiO2, and ITO was perfomed during the 4 years of the project. The suports were also catalyzed by deposition of Pt and tested for its performance and electrochemical stability in RDE and fuel cell experiments. For testing the electrochemical stability and fuel cell performance of the catalysts and supports, we have employed the protocols in use at the Department of Energy and Nissan Technological Center North America (NTCNA). The use of such procedures allows a precise and reproducible estimation of the performance and stability ofmore » the materials and permits comparisons among laboratories and DOE funded projects. RuO2-SiO2 catalyst supports showed no loss in surface area during start-stop stability tests that were performed by cycling the electrode potential between 0 V to 1.8 V for 1000 cycles. Catalyzed support (40% Pt/RuO2-SiO2; 1:1 mole ratio) were tested in a PEFC, resulting in a current density of 750 mA/cm2 at 0.6 Volts, and a maximum power density of 570 mW/cm2. Measurements were conducted at 80 ºC with 75% relative humidity of the inlet gases (H2/O2); Pt loadings were 0.4 mg/cm2 at the cathode and 0.2 mg/cm2 at the anode. Start-stop stability tests for support and catalyzed support performed in RDE and PEFC set-ups have confirmed RuO2-TiO2 support stability. The beginning of life performance was exactly equal to end of life performance (in an MEA that has been subjected to severe start-stop cycling for 10,000 start/stop cycles between 1 V to 1.5 V). This result was in sharp contrast to baseline Pt/C catalyst that showed significant performance deterioration after accelerated stability tests. The Pt/TRO showed minimal loss in performance upon exposure to start-stop cycles. The loss in cell voltage at 1 A/cm2 at 100% RH was almost 700 mV for Pt/C whereas it was only ca. 15 mV for Pt/TRO. 40% RH data (of inlet gases) revealed a similar trend in terms of stability – exceptional stability for Pt/TRO as opposed to very poor stability for Pt/HSAC. These observations were attributed to the much higher stability of the TRO support compared to Carbon. The carbon dioxide concentration in the cathode exit stream during the accelerated degradation test with Pt/TRO (start-stop protocol) was extremely low (between 3 to 10 ppm of CO2). In contrast, the CO2 emission levels from a conventional Pt/C catalyst were found to be approx. 200 ppm. This observation was a clear indicator that the main source of carbon being oxidized to carbon dioxide in an MEA was the carbon catalyst support, and not the gas diffusion layer or the graphite flow fields. Indium tin oxide (ITO) was also evaluated as a catalyst support for PEFCs. Pt/ITO was very stable under start-up/shutdown accelerated degradation protocol (RDE tests in perchloric acid). The ECSA change was less than 4% over 10,000 cycles. The load cycling accelerated protocol (from 0.6 to 0.95 V vs. RHE) resulted in a loss of approximately 34% of the initial ECSA after 10,000 cycles. However, fuel cell testing resulted in a very low performing catalyst. XPS spectroscopy was employed to investigate the changes in the catalysts occuring during fuel cell operation. It was observed a shift of In 3d5/2 and In 3d3/2 peaks towards higher binding energies. This can be explained by the formation of hydroxides or oxy-hydroxides in the surface of the catalyst. O1s spectrum for Pt/ITO catalyst after being operated in the fuel cell, also confirmed the formation of significant amounts of surface hydroxides (12 to 16%). The presence of surface hydroxides in the catalyst increased the electrode resistivity affecting fuel cell performance. NTCNA performed a detailed analysis of transport phenomena (reactants and products to/from the Pt active sites) in both commercial catalyst and Pt/RTO (in order to have a better understanding at the basic level). The proton resistance (Rionomer) in Pt/C and Pt/RTO cathode catalyst layers were 150 and 12 mΩ-cm2, respectively. Pt/RTO catalyst layer has about an order or magnitude lower proton transfer resistance than Pt/C catalyst layer. Since the ionomer/support ratio that was used in formulating the ink for both catalysts was the same (0.9), it is expected that the volumetric coverage of ionomer of both catalysts will be significantly different due to the disparity in the surface areas (Pt/C had ~ 800 m2/g, while Pt/RTO had ~ 50 m2/g). The differences in the ionomer volumetric coverage and the ionomer film thickness may explain the significantly higher proton conductivity in the Pt/RTO catalyst layer when compared to Pt/HSAC. It is therefore very important to optimize the ionomer loadings when synthesizing new catalyst supports (and never rely on values for carbon-based commercial catalysts). Finally, NTCNA has elaborated a cost model for non-carbon support materials considering their durability benefits. Material costs for production of Pt/ RuO2-TiO2 electrodes were compared to Pt/C. RuO2-TiO2 support was more expensive than carbon but the total material cost was still dominated by platinum cost. Though ruthenium is considered a precious metal, its cost is far less than platinum. It should also be noted that ruthenium only makes up 38% of the mass of the support, while the rest is inexpensive TiO2. After considering the durability advantages of Pt/RTO, cost model showed that even with almost double the Pt loading (0.35 vs 0.18 mgPt/cm2), Pt/RTO ($22.7/kWnet) is only slightly more expensive than Pt/C ($21.9/kWnet).« less

Idaho National Laboratory Quarterly Occurrence Analysis 4th Quarter FY 2016

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

Mitchell, Lisbeth Ann

This report is published quarterly by the Idaho National Laboratory (INL) Quality and Performance Management Organization. The Department of Energy (DOE) Occurrence Reporting and Processing System, as prescribed in DOE Order 232.2, “Occurrence Reporting and Processing of Operations Information,” requires a quarterly analysis of events, both reportable and not reportable, for the previous 12 months. This report is the analysis of 84 reportable events (29 from the 4th quarter fiscal year 2016 and 55 from the prior three reporting quarters), as well as 39 other issue reports (including events found to be not reportable and Significant Category A and Bmore » conditions) identified at INL during the past 12 months (two from this quarter and 37 from the prior three quarters).« less

Life expectancy and national income in Europe, 1900-2008: an update of Preston's analysis.

PubMed

Mackenbach, Johan P; Looman, Caspar Wn

2013-08-01

In the past, upward shifts of the so-called Preston curve, which relates life expectancy to national income, have contributed importantly to worldwide increases in life expectancy. These shifts were due to rapid diffusion of knowledge and technology for infectious disease control from high-income to low-income countries. We assessed to what extent life expectancy growth in Europe has been accompanied by upward shifts in the relation between national income and life expectancy in later parts of the 20th century, when progress in cardiovascular disease control was the main driver of life expectancy growth. Data on national income (gross domestic product per capita, in 1990 international dollars), life expectancy and cause-specific mortality covering the period 1900-2008 were extracted from international data banks. (Change in) life expectancy and age-standardized mortality was regressed on (change in) national income, and the regression parameters were used to estimate the contribution to rising life expectancy and declining mortality in Europe as a whole of changes in national income vs shifts in the relation between national income and health outcomes. Large upward shifts in the relation between national income and life expectancy only occurred before 1960, and were due to rapid declines in mortality from infectious diseases which were independent of rises in national income. These shifts account for between two-thirds and four-fifths of the increase in life expectancy in Europe as a whole during this period. After 1960, upward shifts in the relation between national income and life expectancy were much smaller, and contributed only between one-quarter and one-half to the increase in life expectancy in Europe as a whole. During the latter period, declines in mortality from cardiovascular disease were mainly attributable to increases in national income. In contrast to earlier periods, recent life expectancy growth in European countries appears to have been dependent on their economic growth. More rapid diffusion of knowledge and technology for cardiovascular disease control from higher- to lower-income countries in Europe may be needed to close the East-West life expectancy gap, but it is unlikely that this can be achieved in the absence of more equal economic conditions.

Quarterly environmental data summary for first quarter 1999

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

NONE

In support of the Weldon Spring Site Remedial Action Project Federal Facilities Agreement, a copy of the Quarterly Environmental Data Summary (QEDS) for the first quarter of 1999 is enclosed. The data presented in this constitute the QEDS. The data, except for air monitoring data and site KPA generated data (uranium analyses), were received from the contract laboratories, verified by the Weldon Spring Site verification group and merged into the database during the first quarter of 1999. KPA results for on-site total uranium analyses performed during first quarter 1999 are included. Air monitoring data presented are the most recent completemore » sets of quarterly data.« less

Direct catalytic conversion of methane and light hydrocarbon gases. Quarterly report No. 9, October 1--December 31, 1988

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

Wilson, R.B. Jr.; Posin, B.M.; Chan, Yee Wai

The goal of this research is to develop catalysts that directly convert methane and light hydrocarbons to intermediates that later can be converted to either liquid fuels or value-added chemicals, as economics dictate. During this reporting period, we completed our IR spectroscopic examination of the Ru{sub 4}/MgO and FeRu{sub 3}/MgO systems under nitrogen and methane by examining FeRu{sub 3}/MgO under methane. This system behaved quite differently than the same system under nitrogen. Under methane, only one very broad peak is observed at room temperature. Upon heating, the catalyst transformed so that by 300{degrees}C, the spectrum of FeRu{sub 3}/MgO under methanemore » was the same as that of Ru{sub 4}/MgO. This suggests that methane promotes the segregation of the metals in the mixed metal system. The differences in catalytic activity between the FeRu{sub 3}/MgO and Ru{sub 4}/MgO systems may then be due to the presence of IR transparent species such as iron ions which cause different nucleation in the ruthenium clusters. We examined several systems for activity in the methane dehydrogenation reaction. Focusing on systems which produce C{sub 6} hydrocarbons since this is the most useful product. These systems all displayed low activity so that the amount of hydrocarbon product is very low. Some C{sub 6} hydrocarbon is observed over zeolite supports, but its production ceases after the first few hours of reaction. We prepared a new system, Ru{sub 4} supported on carbon, and examined its reactivity. Its activity was very low and in fact the carbon support had the same level of activity. We synthesized four new systems for examination as catalysts in the partial oxidation of methane. Three of these (PtTSPC/MgO, PtTSPC and PdTSPC on carbon) are analogs of PdTSPC/MgO. This system is of interest because we have observed the production of ethane from methane oxidation over PdTSPC/MgO at relatively low temperatures and we wished to explore its generality among close analogs.« less

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)

78 FR 23903 - Proposed Information Collection; Comment Request; Quarterly Summary of State and Local Government...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-04-23

... Quarterly Summary of State and Local Government Tax Revenue, using the F-71 (Quarterly Survey of Property Tax Collections), F-72 (Quarterly Survey of State Tax Collections), and F-73 (Quarterly Survey of Non... data for individual states. The information contained in this survey is the most current information...

29 CFR 548.306 - Average earnings for year or quarter year preceding the current quarter.

Code of Federal Regulations, 2011 CFR

2011-07-01

... PAY Interpretations Authorized Basic Rates § 548.306 Average earnings for year or quarter year... regular rates of pay during the current quarter year, and (ii) such average hourly remuneration during the... 29 Labor 3 2011-07-01 2011-07-01 false Average earnings for year or quarter year preceding the...

2. View to northeast showing quarters and outbuildings, L to ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

2. View to northeast showing quarters and outbuildings, L to R: Service Building (HABS No. VA-1287-D), Medical Officer's Quarters C (in background), Garage (HABS No. VA-1287-F), and Medical Officer's Quarters B - Portsmouth Naval Hospital, Medical Officer's Quarters C, West side Williamson Drive, 400 feet South of Rixey Drive, Portsmouth, Portsmouth, VA

Adjustment Notes for Apprentice and Trainee Estimates: December Quarter 2014. Support Document

ERIC Educational Resources Information Center

National Centre for Vocational Education Research (NCVER), 2015

2015-01-01

Apprentice and trainee data are reported by the State and Territory Training Authorities to National Centre for Vocational Education Research (NCVER) on a quarterly basis, starting at the September quarter of 1994. The set of data submitted that quarter is referred to as Collection 1. The sets of data submitted in subsequent quarters are referred…

Reaction and catalyst engineering to exploit kinetically controlled whole-cell multistep biocatalysis for terminal FAME oxyfunctionalization.

PubMed

Schrewe, Manfred; Julsing, Mattijs K; Lange, Kerstin; Czarnotta, Eik; Schmid, Andreas; Bühler, Bruno

2014-09-01

The oxyfunctionalization of unactivated C−H bonds can selectively and efficiently be catalyzed by oxygenase-containing whole-cell biocatalysts. Recombinant Escherichia coli W3110 containing the alkane monooxygenase AlkBGT and the outer membrane protein AlkL from Pseudomonas putida GPo1 have been shown to efficiently catalyze the terminal oxyfunctionalization of renewable fatty acid methyl esters yielding bifunctional products of interest for polymer synthesis. In this study, AlkBGTL-containing E. coli W3110 is shown to catalyze the multistep conversion of dodecanoic acid methyl ester (DAME) via terminal alcohol and aldehyde to the acid, exhibiting Michaelis-Menten-type kinetics for each reaction step. In two-liquid phase biotransformations, the product formation pattern was found to be controlled by DAME availability. Supplying DAME as bulk organic phase led to accumulation of the terminal alcohol as the predominant product. Limiting DAME availability via application of bis(2-ethylhexyl)phthalate (BEHP) as organic carrier solvent enabled almost exclusive acid accumulation. Furthermore, utilization of BEHP enhanced catalyst stability by reducing toxic effects of substrate and products. A further shift towards the overoxidized products was achieved by co-expression of the gene encoding the alcohol dehydrogenase AlkJ, which was shown to catalyze efficient and irreversible alcohol to aldehyde oxidation in vivo. With DAME as organic phase, the aldehyde accumulated as main product using resting cells containing AlkBGT, AlkL, as well as AlkJ. This study highlights the versatility of whole-cell biocatalysis for synthesis of industrially relevant bifunctional building blocks and demonstrates how integrated reaction and catalyst engineering can be implemented to control product formation patterns in biocatalytic multistep reactions. © 2014 Wiley Periodicals, Inc.

Applying Molecular Bonding Concepts to the Solid State

NASA Astrophysics Data System (ADS)

Dunnington, Benjamin D.

In this thesis, we describe the extension and application of Natural Bond Orbital (NBO) analysis to periodic systems. This enables the translation of rigorous, quantum mechanical calculation results of solid systems into the localized lone pairs and two-center bonds of Lewis structures. Such localized bonding descriptions form the basic language of chemistry, and application of these ideas to solids allows for the understanding of complex phenomena in bulk systems using readily accessible concepts from molecular science. In addition to the algorithmic adjustments needed for to account for periodic boundary conditions in the NBO process, we also discuss methodology to interface the ubiquitous plane wave basis sets of the solid state with the atom-centered basis functions needed as input for NBO analysis. We will describe one method using projection of the plane wave eigenstates, and a second projection-free method that involves the direct calculation of matrix elements of the plane wave Hamiltonian in an atom-centered basis. The reliance of many localized, post-computational analysis techniques on an atom-centered description of the orbitals, means these interfaces will have applicability beyond our NBO development. An ideal area for application of such molecular descriptions of periodic systems is heterogeneous catalysis, where reactants from a gas/liquid phase react on a solid catalyst surface. Previous studies of these systems have originated from the delocalized perspective of the bulk catalyst. NBO provides an explicit description of the perturbative effect of the catalyst on the covalent bonds of the reactant, which is correlated with the catalytic activity of the material. Such a shift to an adsorbate focused description of surface reactivity will enable understanding of catalysis across a variety of materials.

Photocatalytic oxidation of organic dyes with visible-light-driven codoped TiO2 photocatalysts

NASA Astrophysics Data System (ADS)

Zhang, Dongfang; Zeng, Fanbin

2011-06-01

A novel copper (II) and zinc (II) codoped TiO2 photocatalyst was synthesized by a modified sol-gel method using titanium (IV) isopropoxide, Zn(NO3)2 · 6H2O and copper(Il) nitrate as precursors. The samples were characterized by X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS) and photo-luminescence spectra (PL). The XRD results showed undoped and Zn, Cu-codoped TiO2 nanoparticles mainly including anatase phase and a tiny amount of Zn- and Cu-oxides exist in the mixed system, which is attributed to the decomposition of copper and zinc nitrates in the TiO2 gel to form CuO and ZnO and randomly dispersed on the TiO2 surface. On the basis of the optical characterization results, we found that the codoping of copper (II) and zinc (II) resulted a red shift of adsorption and lower recombination probability between electrons and holes, which were the reasons for high photocatalytic activity of Zn, Cu-codoped TiO2 nanoparticles under visible light (λ > 400 nm). The photocatalytic activity of samples was tested for degradation of methyl orange (MO) in solutions. The results indicated that the visible-light driven capability of the codoped catalyst were much higher than that of the pure TiO2 catalyst under visible irradiation. Because of the synergetic effect of copper (II) and zinc (II) element, the Zn, Cu-codoped TiO2 catalyst will show higher quantum yield and enhance absorption of visible light. In the end, a key mechanism was proposed in order to account for the enhanced activity.

Effect of K loadings on nitrate formation/decomposition and on NOx storage performance of K-based NOx storage-reduction catalysts

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

Kim, Do Heui; Mudiyanselage, Kumudu K.; Szanyi, Janos

2013-10-25

We have investigated nitrate formation and decomposition processes, and measured NOx storage performance on Pt-K2O/Al2O3 catalysts as a function of potassium loading. After NO2 adsorption at room temperature, ionic and bidentate nitrates were observed by fourier transform infra-red (FTIR) spectroscopy. The ratio of the former to the latter species increased with increasing potassium loading up to 10 wt%, and then stayed almost constant with additional K, demonstrating a clear dependence of loading on the morphology of the K species. Although both K2O(10)/Al2O3 and K2O(20)/Al2O3 samples have similar nitrate species after NO2 adsorption, the latter has more thermally stable nitrate speciesmore » as evidenced by FTIR and NO2 temperature programmed desorption (TPD) results. With regard to NOx storage performance, the temperature of maximum NOx uptake (Tmax) is 573 K up to a potassium loading of 10 wt%. As the potassium loading increases from 10 wt% to 20 wt%, Tmax shifted from 573 K to 723 K. Moreover, the amount of NO uptake (38 cm3 NOx/g catal) at Tmax increased more than three times, indicating that efficiency of K in storing NOx is enhanced significantly at higher temperature, in good agreement with the NO2 TPD and FTIR results. Thus, a combination of characterization and NOx storage performance results demonstrates an unexpected effect of potassium loading on nitrate formation and decomposition processes; results important for developing Pt-K2O/Al2O3 for potential applications as high temperature NOx storage-reduction catalysts.« less

Variation in the composition of selected milk fraction samples from healthy and mastitic quarters, and its significance for mastitis diagnosis.

PubMed

Bansal, Baljinder K; Hamann, Joern; Grabowskit, Nils Th; Singh, Krishan B

2005-05-01

Seven variables--electrical conductivity (EC), somatic cell count (SCC), N-acetyl-beta-D-glucosaminidase (NAGase), lactose, protein, fat and pH--were compared in four quarter milk fractions (MF1: strict foremilk; MF2: first 12-15 ml foremilk; MF3: subsequent 40-45 ml milk; MF4: strippings) and in one cow composite milk sample (CC) per cow. The study used 142 quarters from 37 lactating cows of the German Black Pied breed. To rule out any possible effect due to management, animal physiology and analytical procedures, the collection and processing of milk samples from each cow was repeated for three consecutive days, and the means of 3-d values were used. All variables were affected significantly by milk fraction and udder health. Compared with foremilk, EC, lactose and protein levels in strippings decreased, while SCC, NAGase and fat increased. The pH of foremilk and strippings did not differ significantly in healthy or in mastitic quarters. The difference between MF1 and MF2 was significant for EC in mastitic quarters, and for SCC in healthy quarters only. In general, mastitis resulted in a significant increase in EC, SCC, NAGase and protein but in a decrease in lactose and fat contents of milk in one or more of the milk fractions studied. Comparison of cow composite milk samples from healthy and mastitic cows revealed the significance (P < 0.01) of udder health for EC, SCC and lactose. Of the different parameters that can distinguish between healthy and mastitic quarters or cows, EC could be used to classify 76% of quarters and 73% of cows correctly, while the lactose content permitted correct identification of 81% of quarters and 76% of cows. NAGase and pH could be used to determine the status of 73% and 61% of quarters, respectively. In general, the correlation observed in strippings was higher than in foremilk for almost all the variables studied. Surprisingly, EC, SCC, NAGase and lactose in milk from healthy quarters of mastitic cows (with at least one mastitic quarter) differed significantly (P < 0.05) from those from healthy quarters of cows with all four healthy quarters, indicating an inconsistent effect of mastitic quarters on neighbouring healthy quarters (quarter interdependence).

Cell module and fuel conditioner

NASA Technical Reports Server (NTRS)

Hoover, D. Q., Jr.

1980-01-01

Measurements of stack height changes with temperature and cell material characteristics were made. Stack 559 was assembled and components were fabricated for 560, 561, and 562. Stack 425 was transferred from the parallel DOE program and installed in the OS/IES simulation loop for mechanical and electrical testing. Construction and preliminary checkout of the 2 kW test facility was completed and design and procurement of the 8 kW test facility was initiated. The fuel conditioning subsystem design continued to evolve and the state points for the current design were calculated at full and part load conditions. Steam reforming catalyst activity tests were essentially completed and aging tests and CO shift converter tests were initiated.

Controlling reactivity of nanoporous catalyst materials by tuning reaction product-pore interior interactions: Statistical mechanical modeling

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

Wang, Jing; Ackerman, David M.; Lin, Victor S.-Y.

2013-04-02

Statistical mechanical modeling is performed of a catalytic conversion reaction within a functionalized nanoporous material to assess the effect of varying the reaction product-pore interior interaction from attractive to repulsive. A strong enhancement in reactivity is observed not just due to the shift in reaction equilibrium towards completion but also due to enhanced transport within the pore resulting from reduced loading. The latter effect is strongest for highly restricted transport (single-file diffusion), and applies even for irreversible reactions. The analysis is performed utilizing a generalized hydrodynamic formulation of the reaction-diffusion equations which can reliably capture the complex interplay between reactionmore » and restricted transport.« less

Cryogenic hydrogen-induced air-liquefaction technologies for combined-cycle propulsion applications

NASA Technical Reports Server (NTRS)

Escher, William J. D.

1992-01-01

Given here is a technical assessment of the realization of cryogenic hydrogen induced air liquefaction technologies in a prospective onboard aerospace vehicle process setting. The technical findings related to the status of air liquefaction technologies are reviewed. Compact lightweight cryogenic heat exchangers, heat exchanger atmospheric constituent fouling alleviation measures, para/ortho-hydrogen shift-conversion catalysts, cryogenic air compressors and liquid air pumps, hydrogen recycling using slush hydrogen as a heat sink, liquid hydrogen/liquid air rocket-type combustion devices, and technically related engine concepts are discussed. Much of the LACE work is related to aerospaceplane propulsion concepts that were developed in the 1960's. Emphasis is placed on the Liquid Air Cycle Engine (LACE).

Effect of ZnO facet on ethanol steam reforming over Co/ZnO

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

Yu, Ning; Zhang, He; Davidson, Stephen D.

2016-01-01

The effects of ZnO facets on ethanol steam reforming (ESR) were investigated over Co/ZnO catalysts synthesized using ZnO with different fractions of (10-10) non-polar facet. Co supported on ZnO with a higher fraction of (10-10) non-polar facet shows higher C-C cleavage activity and higher selectivity to CO2 (lower selectivity to CO) compared with Co supported on ZnO with less (10-10) non-polar facet exposed. The improved ethanol steam reforming performances are attributed to the high fraction of metallic Co stabilized by the ZnO (10-10) non-polar facet, which enhanced C-C cleavage and water-gas-shift (WGS) activities.

1. CARRIAGE HOUSE (left) AND SLAVE QUARTERS, SOUTH FRONT. A ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

1. CARRIAGE HOUSE (left) AND SLAVE QUARTERS, SOUTH FRONT. A kitchen was included in the quarters. - Charles Fraser House, Carriage House & Slave Quarters, 55 King Street, Charleston, Charleston County, SC

EMSL Quarterly Highlights Report: 1st Quarter, Fiscal Year 2009

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

Showalter, Mary Ann; Kathmann, Loel E.; Manke, Kristin L.

2009-02-02

The EMSL Quarterly Highlights Report covers the science, staff and user recognition, and publication activities that occurred during the 1st quarter (October 2008 - December 2008) of Fiscal Year 2009.

Idaho National Laboratory Quarterly Occurrence Analysis for the 1st Quarter FY2017

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

Mitchell, Lisbeth Ann

This report is published quarterly by the Idaho National Laboratory (INL) Quality and Performance Management Organization. The Department of Energy (DOE) Occurrence Reporting and Processing System (ORPS), as prescribed in DOE Order 232.2, “Occurrence Reporting and Processing of Operations Information,” requires a quarterly analysis of events, both reportable and not reportable, for the previous 12 months. This report is the analysis of 82 reportable events (13 from the 1st quarter (Qtr) of fiscal year (FY) 2017 and 68 from the prior three reporting quarters), as well as 31 other issue reports (including events found to be not reportable and Significantmore » Category A and B conditions) identified at INL during the past 12 months (seven from this quarter and 24 from the prior three quarters).« less

Notable deals in the pharmaceutical industry in the first quarter of 2017.

PubMed

Cruces, E

2017-06-01

During the first quarter of 2017, Cortellis Competitive Intelligence had 1,073 new deals added as part of its ongoing coverage of pharmaceutical licensing activity. This meant a slight increase on the last quarter (1,022) and a similar volume on the same quarter for the previous 1 year (1,141). However, this quarter showed a significant augment in deals worth more than USD 0.5 billion on the last quarter (17 vs. 12). This article will focus on highlighting a number of the most valuable and notable deals forged during the quarter, as well as a selection of deals from some of the most prolific deal makers. An update on milestone, options and terminated deals of significance will also be presented, along with an early outlook on the next quarter's pharmaceutical licensing activity.

Adjustment Notes for Apprentice and Trainee Estimates: December Quarter 2016. Support Document

ERIC Educational Resources Information Center

National Centre for Vocational Education Research (NCVER), 2017

2017-01-01

Apprentice and trainee data are reported by the State and Territory Training Authorities to NCVER on a quarterly basis, starting at the September quarter of 1994. The set of data submitted that quarter is referred to as Collection 1. The sets of data submitted in subsequent quarters are referred to as Collection 2, Collection 3 and so on. NCVER…

Adjustment Notes for Apprentice and Trainee Estimates: September Quarter 2016. Support Document

ERIC Educational Resources Information Center

National Centre for Vocational Education Research (NCVER), 2017

2017-01-01

Apprentice and trainee data are reported by the State and Territory Training Authorities to NCVER on a quarterly basis, starting at the September quarter of 1994. The set of data submitted that quarter is referred to as Collection 1. The sets of data submitted in subsequent quarters are referred to as Collection 2, Collection 3 and so on. NCVER…

From Lab to Fab: Developing a Nanoscale Delivery Tool for Scalable Nanomanufacturing

NASA Astrophysics Data System (ADS)

Safi, Asmahan A.

The emergence of nanomaterials with unique properties at the nanoscale over the past two decades carries a capacity to impact society and transform or create new industries ranging from nanoelectronics to nanomedicine. However, a gap in nanomanufacturing technologies has prevented the translation of nanomaterial into real-world commercialized products. Bridging this gap requires a paradigm shift in methods for fabricating structured devices with a nanoscale resolution in a repeatable fashion. This thesis explores the new paradigms for fabricating nanoscale structures devices and systems for high throughput high registration applications. We present a robust and scalable nanoscale delivery platform, the Nanofountain Probe (NFP), for parallel direct-write of functional materials. The design and microfabrication of NFP is presented. The new generation addresses the challenges of throughput, resolution and ink replenishment characterizing tip-based nanomanufacturing. To achieve these goals, optimized probe geometry is integrated to the process along with channel sealing and cantilever bending. The capabilities of the newly fabricated probes are demonstrated through two type of delivery: protein nanopatterning and single cell nanoinjection. The broad applications of the NFP for single cell delivery are investigated. An external microfluidic packaging is developed to enable delivery in liquid environment. The system is integrated to a combined atomic force microscope and inverted fluorescence microscope. Intracellular delivery is demonstrated by injecting a fluorescent dextran into Hela cells in vitro while monitoring the injection forces. Such developments enable in vitro cellular delivery for single cell studies and high throughput gene expression. The nanomanufacturing capabilities of NFPs are explored. Nanofabrication of carbon nanotube-based electronics presents all the manufacturing challenges characterizing of assembling nanomaterials precisely onto devices. The presented study combines top-down and bottom-approaches by integrating the catalyst patterning and carbon nanotube growth directly on structures. Large array of iron-rich catalyst are patterned on an substrate for subsequent carbon nanotubes synthesis. The dependence of probe geometry and substrate wetting is assessed by modeling and experimental studies. Finally preliminary results on synthesis of carbon nanotube by catalyst assisted chemical vapor deposition suggest increasing the catalyst yield is critical. Such work will enable high throughput nanomanufacturing of carbon nanotube based devices.

Variation in the Asian monsoon intensity and dry-wet conditions since the Little Ice Age in central China revealed by an aragonite stalagmite

NASA Astrophysics Data System (ADS)

Yin, J.-J.; Yuan, D.-X.; Li, H.-C.; Cheng, H.; Li, T.-Y.; Edwards, R. L.; Lin, Y.-S.; Qin, J.-M.; Tang, W.; Zhao, Z.-Y.; Mii, H.-S.

2014-10-01

This paper focuses on the climate variability in central China since AD 1300, involving: (1) a well-dated, 1.5-year resolution stalagmite δ18O record from Lianhua Cave, central China (2) links of the δ18O record with regional dry-wet conditions, monsoon intensity, and temperature over eastern China (3) correlations among drought events in the Lianhua record, solar irradiation, and ENSO (El Niño-Southern Oscillation) variation. We present a highly precise, 230Th / U-dated, 1.5-year resolution δ18O record of an aragonite stalagmite (LHD1) collected from Lianhua Cave in the Wuling Mountain area of central China. The comparison of the δ18O record with the local instrumental record and historical documents indicates that (1) the stalagmite δ18O record reveals variations in the summer monsoon intensity and dry-wet conditions in the Wuling Mountain area. (2) A stronger East Asian summer monsoon (EASM) enhances the tropical monsoon trough controlled by ITCZ (Intertropical Convergence Zone), which produces higher spring quarter rainfall and isotopically light monsoonal moisture in the central China. (3) The summer quarter/spring quarter rainfall ratio in central China can be a potential indicator of the EASM strength: a lower ratio corresponds to stronger EASM and higher spring rainfall. The ratio changed from <1 to >1 after 1950, reflecting that the summer quarter rainfall of the study area became dominant under stronger influence of the Northwestern Pacific High. Eastern China temperatures varied with the solar activity, showing higher temperatures under stronger solar irradiation, which produced stronger summer monsoons. During Maunder, Dalton and 1900 sunspot minima, more severe drought events occurred, indicating a weakening of the summer monsoon when solar activity decreased on decadal timescales. On an interannual timescale, dry conditions in the study area prevailed under El Niño conditions, which is also supported by the spectrum analysis. Hence, our record illustrates the linkage of Asian summer monsoon precipitation to solar irradiation and ENSO: wetter conditions in the study area under stronger summer monsoon during warm periods, and vice versa. During cold periods, the Walker Circulation will shift toward the central Pacific under El Niño conditions, resulting in a further weakening of Asian summer monsoons.

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.

Notable licensing deals in the biopharma industry in the second quarter of 2017.

PubMed

D'Souza, P

2017-08-01

During the second quarter of 2017, Cortellis Competitive Intelligence added 967 new licensing deals (excluding mergers and acquisition deals) as part of its ongoing coverage of pharmaceutical licensing activity. This meant an 8% decrease on the previous quarter (1,050) and a 3% decrease from the same quarter in 2016 (993). This quarter also showed a significant decline in the number of deals worth more than USD 0.5 billion from the last quarter (7 vs. 17). This article will highlight a number of the most valuable and notable deals forged during the quarter, as well as a selection of deals from some of the most prolific deal makers in the life sciences. An update on milestone, options and terminated deals of significance will also be presented, along with an early outlook on the next quarter's pharmaceutical licensing activity.

Design and chemical synthesis of iodine-containing molecules for application to solar-pumped I* lasers

NASA Technical Reports Server (NTRS)

Shiner, C. S.

1986-01-01

The design and chemical synthesis of new media for solar pumped iodine molecule lasers are explored. In an effort to prepare an iodo fluorocarbon compound absorbing strongly at 300 nm or above, the synthesis of perfluoro allylic iodides was investigated. These compounds furnish especially stable allylic radicals upon photodissociation. The desired red shift is anticipated in the absorption maximum could correlate with increasing radical stability. This expectation was based upon the analysis, previously reported, of the structures and absorption maxima of compounds studied earlier. A previously unknown substance was prepared, a prototypical target molecule, perfluoro-3-iodocyclopent-1-ene. It was obtained by reaction of perfluorocyclopentene with sulfur trioxide under the influence of antimony pentafluoride catalyst, followed by treatment of the resulting allylic fluorosulfonate with sodium iodide in sulfoland solvent. Preliminary data indicate that the absorption maximum for the iodo fluorocarbon is not shifted significantly to longer wavelength. It is not certain whether this result reflects an unexpected influence of the cyclic structure upon the position of the absorption maximum.

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.

42 CFR 433.10 - Rates of FFP for program services.

Code of Federal Regulations, 2013 CFR

2013-10-01

...; (B) 95 percent, for calendar quarters in CY 2017; (C) 94 percent, for calendar quarters in CY 2018... quarters in CY 2018; and (F) 100 percent, for calendar quarters in CY 2019 and all subsequent calendar...

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.

Experimental intramammary inoculation with Mycoplasma bovis in vaccinated and unvaccinated cows: effect on milk production and milk quality.

PubMed Central

Boothby, J T; Jasper, D E; Thomas, C B

1986-01-01

The effect of vaccination on milk production was evaluated in vaccinated and control cows experimentally challenged in two of four quarters with live Mycoplasma bovis. During the first three weeks after experimental challenge, six of eight unchallenged quarters on vaccinated cows and seven of eight unchallenged quarters on control cows became infected. Most of these quarters secreted normal milk, with negative California Mastitis Test scores and maintained normal milk production throughout most of the study (although some quarters on control cows remained infected). All challenged quarters became infected, had strong California Mastitis Test reactions, and had a drastic (greater than 85%) loss in milk production. Thereafter, four of eight challenged quarters on control cows remained infected, had mostly positive California Mastitis Test scores, produced mostly normal-appearing milk, and recovered some productive capabilities. By the end of the study no M. bovis could be recovered from challenged quarters on vaccinated cows and the milk appeared mostly normal. The California Mastitis Test scores on these quarters, however, remained elevated and milk production remained very low. PMID:3756674

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.

Hawaiian volcano observatory summary 103; Part I, seismic data, January to December 2003

USGS Publications Warehouse

Nakata, Jennifer S.; Heliker, C.; Orr, T.; Hoblitt, R.

2004-01-01

The Hawaiian Volcano Observatory (HVO) summary presents seismic data gathered during the year and a chronological narrative describing the volcanic events. The seismic summary is offered without interpretation as a source of preliminary data. It is complete in the sense that most data for events of M= 1.5 routinely gathered by the Observatory are included. The emphasis in collection of tilt and deformation data has shifted from quarterly measurements at a few water-tube tilt stations ('wet' tilt) to a larger number of continuously recording borehole tiltmeters, repeated measurements at numerous spirit-level tilt stations ('dry' tilt), and surveying of level and trilateration networks. Because of the large quantity of deformation data now gathered and differing schedules of data reduction, the seismic and deformation summaries are published separately. The HVO summaries have been published in various forms since 1956. Summaries prior to 1974 were issued quarterly, but cost, convenience of preparation and distribution, and the large quantities of data dictated an annual publication beginning with Summary 74 for the year 1974. Summary 86 (the introduction of CUSP at HVO) includes a description of the seismic instrumentation, calibration, and processing used in recent years. The present summary includes background information on the seismic network and processing to allow use of the data and to provide an understanding of how they were gathered.

Hawaiian Volcano Observatory summary 100; Part 1, seismic data, January to December 2000

USGS Publications Warehouse

Nakata, Jennifer S.

2001-01-01

The Hawaiian Volcano Observatory (HVO) summary presents seismic data gathered during the year and a chronological narrative describing the volcanic events. The seismic summary is offered without interpretation as a source of preliminary data. It is complete in the sense that all data for events of M≥1.5 routinely gathered by the Observatory are included. The emphasis in collection of tilt and deformation data has shifted from quarterly measurements at a few water-tube tilt stations (“wet” tilt) to a larger number of continuously recording borehole tiltmeters, repeated measurements at numerous spirit-level tilt stations (“dry” tilt), and surveying of level and trilateration networks. Because of the large quantity of deformation data now gathered and differing schedules of data reduction, the seismic and deformation summaries are published separately. The HVO summaries have been published in various forms since 1956. Summaries prior to 1974 were issued quarterly, but cost, convenience of preparation and distribution, and the large quantities of data dictated an annual publication beginning with Summary 74 for the year 1974. Summary 86 (the introduction of CUSP at HVO) includes a description of the seismic instrumentation, calibration, and processing used in recent years. The present summary includes enough background information on the seismic network and processing to allow use of the data and to provide an understanding of how they were gathered.

Hawaiian Volcano Observatory summary 101: Part 1, seismic data, January to December 2001

USGS Publications Warehouse

Nakata, Jennifer S.; Chronological summary by Heliker, C.

2002-01-01

The Hawaiian Volcano Observatory (HVO) summary presents seismic data gathered during the year and a chronological narrative describing the volcanic events. The seismic summary is offered without interpretation as a source of preliminary data. It is complete in the sense that all data for events of M>1.5 routinely gathered by the Observatory are included. The emphasis in collection of tilt and deformation data has shifted from quarterly measurements at a few water-tube tilt stations ("wet" tilt) to a larger number of continuously recording borehole tiltmeters, repeated measurements at numerous spirit-level tilt stations ("dry" tilt), and surveying of level and trilateration networks. Because of the large quantity of deformation data now gathered and differing schedules of data reduction, the seismic and deformation summaries are published separately. The HVO summaries have been published in various forms since 1956. Summaries prior to 1974 were issued quarterly, but cost, convenience of preparation and distribution, and the large quantities of data dictated an annual publication beginning with Summary 74 for the year 1974. Summary 86 (the introduction of CUSP at HVO) includes a description of the seismic instrumentation, calibration, and processing used in recent years. The present summary includes enough background information on the seismic network and processing to allow use of the data and to provide an understanding of how they were gathered.

Association of the Centers for Medicare & Medicaid Services' National Partnership to Improve Dementia Care With the Use of Antipsychotics and Other Psychotropics in Long-term Care in the United States From 2009 to 2014.

PubMed

Maust, Donovan T; Kim, H Myra; Chiang, Claire; Kales, Helen C

2018-03-17

The Centers for Medicare & Medicaid Services' National Partnership to Improve Dementia Care in Nursing Homes (hereafter referred to as the partnership) was established to improve the quality of care for patients with dementia, measured by the rate of antipsychotic prescribing. To determine the association of the partnership with trends in prescribing of antipsychotic and other psychotropic medication among older adults in long-term care. This interrupted time-series analysis of a 20% Medicare sample from January 1, 2009, to December 31, 2014, was conducted among 637 426 fee-for-service Medicare beneficiaries in long-term care with Part D coverage. Data analysis was conducted from May 1, 2017, to January 9, 2018. Quarterly prevalence of use of antipsychotic and nonantipsychotic psychotropic medications (antidepressants, mood stabilizers [eg, valproic acid and carbamazepine], benzodiazepines, and other anxiolytics or sedative-hypnotics). Among the 637 426 individuals in the study (446 538 women and 190 888 men; mean [SD] age at entering nursing home, 79.3 [12.1] years), psychotropic use was declining before initiation of the partnership with the exception of mood stabilizers. In the first quarter of 2009, a total of 31 056 of 145 841 patients (21.3%) were prescribed antipsychotics, which declined at a quarterly rate of -0.53% (95% CI, -0.63% to -0.44%; P < .001) until the start of the partnership. At that point, the quarterly rate of decline decreased to -0.29% (95% CI, -0.39% to -0.20%; P < .001), a postpartnership slowing of 0.24% per quarter (95% CI, 0.09%-0.39%; P = .003). The use of mood stabilizers was growing before initiation of the partnership and then accelerated after initiation of the partnership (rate, 0.22%; 95% CI, 0.18%-0.25%; P < .001; rate change, 0.14%; 95% CI, 0.10%-0.18%; P < .001), reaching 71 492 of 355 716 patients (20.1%) by the final quarter of 2014. Antidepressants were the most commonly prescribed medication overall: in the beginning of 2009, a total of 75 841 of 145 841 patients (52.0%) were prescribed antidepressants. As with antipsychotics, antidepressant use declined both before and after initiation of the partnership, but the decrease slowed (rate change, 0.34%; 95% CI, 0.18%-0.50%; P < .001). Findings were similar when limited to patients with dementia. Prescribing of psychotropic medications to patients in long-term care has declined, although the partnership did not accelerate this decrease. However, the use of mood stabilizers, possibly as a substitute for antipsychotics, increased and accelerated after initiation of the partnership in both long-term care residents overall and in those with dementia. Measuring use of antipsychotics alone may be an inadequate proxy for quality of care and may have contributed to a shift in prescribing to alternative medications with a poorer risk-benefit balance.

Optimization of pyrochlore catalysts for the dry reforming of methane

NASA Astrophysics Data System (ADS)

Polo Garzon, Felipe

The conversion of methane into syngas (a mixture of CO and H2), which can be further converted into a variety of chemicals and particularly liquid fuels, is of growing importance given recent increases in methane production world-wide. Furthermore, since using CO2 as the co-feed offers many environmental advantages, dry reforming of methane (DRM, CH4 + CO2 [special character omitted] 2CO + 2H 2) has received renewed attention. In recent years, experimentalists have shown that the Rh-substituted lanthanum zirconate pyrochlore (LRhZ) material is catalytically active for DRM, exhibits long-term thermal stability and resists deactivation; however, previous to this doctoral work, a detailed understanding of the reaction mechanism on pyrochlore catalyst surfaces was still scarce, making it difficult to optimize this material. In this work, initial computational efforts employing density functional theory (DFT) showed the plane (111) of the LRhZ crystal structure as the one catalytically active for DRM. In addition, the primary reaction pathway was identified, along with two rate determining steps (RDSs), the CH2 oxygenation step and the CHO dehydrogenation step, which lie on the CH 4 dehydrogenation/oxygenation path. The mechanistic understanding of DRM over LRhZ was further developed using steady-state isotopic transient kinetic analysis (SSITKA). Reversible adsorption of CO2 on the surface was observed, along with short surface residence times (< 0.6 s) at 650 and 800 °C, and increasing turnover frequencies with temperature. Comparisons between isotopic responses supported the DFT-derived reaction mechanism. Furthermore, isotopic transient kinetics confirmed that all metal atoms (Rh, Zr and La) on the surface are involved in the reaction mechanism, as previously pointed by DFT calculations. A DFT-based microkinetic model that predicts the reaction performance at different conditions was built. The model was validated against experimental data, showing remarkable agreement, which further confirmed the reliability of the DFT data. Computational analysis of one of the RDSs (the CHO dehydrogenation step) suggested Pd as an effective co-dopant to reduce the activation barrier of this step. This bimetallic Rh-Pd-substituted lanthanum zirconate pyrochlore (Rh-Pd-LZ) was synthesized, characterized and tested. The Rh-Pd-LZ catalyst successfully increased conversions at high temperatures while providing H 2 to CO ratios close to unity; thus fostering DRM and inhibiting the competing reaction, the reverse water gas shift reaction (RWGS, CO2 + H2 [special character omitted] CO + H2O). The Rh-Pd-LZ catalyst outperformed the initial catalyst, the LRhZ, at high temperatures.

Double air-fuel ratio sensor system having double-skip function

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

Katsuno, T.

1988-01-26

A method for controlling the air-fuel ratio in an internal combustion engine is described having a catalyst converter for removing pollutants in the exhaust gas thereof, and upstream-side and downstream-side air-fuel ratio sensors disposed upstream and downstream, respectively, of the catalyst converter for detecting a concentration of a specific component in an exhaust gas, comprising the steps of: comparing the output of the upstream-side air-fuel ratio sensor with a first predetermined value; gradually changing a first air-fuel ratio correction amount in accordance with a result of the comparison of the output of the upstream-side air-fuel ratio sensor with the predeterminedmore » value; shifting the first air-fuel ratio correction amount by a first skip amount during a predetermined time period after the result of the comparison of the upstream-side air-fuel ratio sensor is changed; shifting the first air-fuel ratio correction amount by a second skip amount smaller than the first skip amount after the predetermined time period has passed; comparing the output of the downstream-side air-fuel ratio with a second predetermined value, calculating a second air-fuel ratio correction amount in accordance with the comparison result of the output of the downstream-side air-fuel ratio sensor with the second predetermined value; and adjusting the actual air-fuel ratio in accordance with the first and second air-fuel ratio correction amounts; wherein the gradually-changing step comprises the steps of: gradually decreasing the first air-fuel ratio correction amount when the output of the upstream-side air-fuel sensor is on the rich side with respect to the first predetermined value; and gradually increasing the first air-fuel ratio correction amount when the output of the upstream-side air-fuel sensor is on the lean side with respect to the first predetermined value.« less

1. GENERAL VIEW OF SLAVE QUARTERS No. 2 (right). Located ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

1. GENERAL VIEW OF SLAVE QUARTERS No. 2 (right). Located north of main house. The building at left is Slave Quarters No. 1 (HABS No. VA-1233 C) - Westend, Slave Quarters No. 2, Route 638 vicinity, Trevilians, Louisa County, VA

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.