Self-assembled diatom substrates with plasmonic functionality

NASA Astrophysics Data System (ADS)

Kwon, Sun Yong; Park, Sehyun; Nichols, William T.

2014-04-01

Marine diatoms have an exquisitely complex exoskeleton that is promising for engineered surfaces such as sensors and catalysts. For such applications, creating uniform arrays of diatom frustules across centimeter scales will be necessary. Here, we present a simple, low-cost floating interface technique to self-assemble the diatom frustules. We show that well-prepared diatoms form floating hexagonal close-packed arrays at the air-water interface that can be transferred directly to a substrate. We functionalize the assembled diatom surfaces with gold and characterize the plasmonic functionality by using surface enhanced Raman scattering (SERS). Thin gold films conform to the complex, hierarchical diatom structure and produce a SERS enhancement factor of 2 × 104. Small gold nanoparticles attached to the diatom's surface produce a higher enhancement of 7 × 104 due to stronger localization of the surface plasmons. Taken together, the large-scale assembly and plasmonic functionalization represent a promising platform to control the energy and the material flows at a complex surface for applications such as sensors and plasmonic enhanced catalysts.

Features of flow around the flying wing model at various attack and slip angle

NASA Astrophysics Data System (ADS)

Pavlenko, A. M.; Zanin, B. Yu.; Katasonov, M. M.

2017-10-01

Experimental study of flow features around aircraft model having "flying wing" form and belonging to the category of small-unmanned aerial vehicleswas carried out. Hot-wire anemometry and flow visualization techniques were used in the investigation to get quantitative data and streamlines pictures ofthe flow near the model surface. Evolution of vortex structures depending on the attack and slip angle was demonstrated. The possibility of flow control and reduction of flow separation zones on the wing surface by means of ledges in the form of cones was also investigated. It was shown, that the laminar-turbulent transition scenario on the flying wing model is identical to the one on a straight wing and occurs through the development of a package of unstable oscillations in the boundary layer separation.

Dual reactor for in situ/operando fluorescent mode XAS studies of sample containing low-concentration 3d or 5d metal elements

NASA Astrophysics Data System (ADS)

Nguyen, Luan; Tang, Yu; Li, Yuting; Zhang, Xiaoyan; Wang, Ding; Tao, Franklin Feng

2018-05-01

Transition metal elements are the most important elements of heterogeneous catalysts used for chemical and energy transformations. Many of these catalysts are active at a temperature higher than 400 °C. For a catalyst containing a 3d or 5d metal element with a low concentration, typically their released fluorescence upon the K-edge or L-edge adsorption of X-rays is collected for the analysis of chemical and coordination environments of these elements. However, it is challenging to perform in situ/operando X-ray absorption spectroscopy (XAS) studies of elements of low-energy absorption edges at a low concentration in a catalyst during catalysis at a temperature higher than about 450 °C. Here a unique reaction system consisting two reactors, called a dual reactor system, was designed for performing in situ or operando XAS studies of these elements of low-energy absorption edges in a catalyst at a low concentration during catalysis at a temperature higher than 450 °C in a fluorescent mode. This dual-reactor system contains a quartz reactor for preforming high-temperature catalysis up to 950 °C and a Kapton reactor remaining at a temperature up to 450 °C for collecting data in the same gas of catalysis. With this dual reactor, chemical and coordination environments of low-concentration metal elements with low-energy absorption edges such as the K-edge of 3d metals including Ti, V, Cr, Mn, Fe, Co, Ni, and Cu and L edge of 5d metals including W, Re, Os, Ir, Pt, and Au can be examined through first performing catalysis at a temperature higher than 450 °C in the quartz reactor and then immediately flipping the catalyst in the same gas flow to the Kapton reactor remained up to 450 °C to collect data. The capability of this dual reactor was demonstrated by tracking the Mn K-edge of the MnOx/Na2WO4 catalyst during activation in the temperature range of 300-900 °C and catalysis at 850 °C.

Model of carbon nanofiber internal structure formation and instability of catalytic growth interface

NASA Astrophysics Data System (ADS)

Merkulov, I. A.; Merkulov, V. I.; Melechko, A. V.; Klein, K. L.; Lowndes, D. H.; Simpson, M. L.

2007-07-01

It is well known that the internal structure determines the properties of carbon nanotubes and carbon nanofibers. However, a fundamental understanding of the processes that drive structure formation is missing, hindering the development of controlled synthesis strategies. Here we use theoretical calculations to explore the time evolution of the shape of the interface between the catalyst nanoparticle and its associated graphitic nanofiber at the initial stages of growth. This phenomenological description of the behavior of the catalyst nanoparticle-graphite interface constructed with model parameters provides new understanding of the mechanisms that control the internal structure of carbon nanofibers. We show that if the magnitude of the interface curvature exceeds a critical value κcrit , the interface loses stability and a cavity forms in the center of the nanofiber.

Semiconductor-Electrocatalyst Interfaces: Theory, Experiment, and Applications in Photoelectrochemical Water Splitting.

PubMed

Nellist, Michael R; Laskowski, Forrest A L; Lin, Fuding; Mills, Thomas J; Boettcher, Shannon W

2016-04-19

Light-absorbing semiconductor electrodes coated with electrocatalysts are key components of photoelectrochemical energy conversion and storage systems. Efforts to optimize these systems have been slowed by an inadequate understanding of the semiconductor-electrocatalyst (sem|cat) interface. The sem|cat interface is important because it separates and collects photoexcited charge carriers from the semiconductor. The photovoltage generated by the interface drives "uphill" photochemical reactions, such as water splitting to form hydrogen fuel. Here we describe efforts to understand the microscopic processes and materials parameters governing interfacial electron transfer between light-absorbing semiconductors, electrocatalysts, and solution. We highlight the properties of transition-metal oxyhydroxide electrocatalysts, such as Ni(Fe)OOH, because they are the fastest oxygen-evolution catalysts known in alkaline media and are (typically) permeable to electrolyte. We describe the physics that govern the charge-transfer kinetics for different interface types, and show how numerical simulations can explain the response of composite systems. Emphasis is placed on "limiting" behavior. Electrocatalysts that are permeable to electrolyte form "adaptive" junctions where the interface energetics change during operation as charge accumulates in the catalyst, but is screened locally by electrolyte ions. Electrocatalysts that are dense, and thus impermeable to electrolyte, form buried junctions where the interface physics are unchanged during operation. Experiments to directly measure the interface behavior and test the theory/simulations are challenging because conventional photoelectrochemical techniques do not measure the electrocatalyst potential during operation. We developed dual-working-electrode (DWE) photoelectrochemistry to address this limitation. A second electrode is attached to the catalyst layer to sense or control current/voltage independent from that of the semiconductor back ohmic contact. Consistent with simulations, electrolyte-permeable, redox-active catalysts such as Ni(Fe)OOH form "adaptive" junctions where the effective barrier height for electron exchange depends on the potential of the catalyst. This is in contrast to sem|cat interfaces with dense electrolyte-impermeable catalysts, such as nanocrystalline IrOx, that behave like solid-state buried (Schottky-like) junctions. These results elucidate a design principle for catalyzed photoelectrodes. The buried heterojunctions formed by dense catalysts are often limited by Fermi-level pinning and low photovoltages. Catalysts deposited by "soft" methods, such as electrodeposition, form adaptive junctions that tend to provide larger photovoltages and efficiencies. We also preview efforts to improve theory/simulations to account for the presence of surface states and discuss the prospect of carrier-selective catalyst contacts.

Supported Dendrimer-Encapsulated Metal Clusters: Toward Heterogenizing Homogeneous Catalysts

DOE PAGES

Ye, Rong; Zhukhovitskiy, Aleksandr V.; Deraedt, Christophe V.; ...

2017-07-13

Recyclable catalysts, especially those that display selective reactivity, are vital for the development of sustainable chemical processes. Among available catalyst platforms, heterogeneous catalysts are particularly well-disposed toward separation from the reaction mixture via filtration methods, which renders them readily recyclable. Furthermore, heterogeneous catalysts offer numerous handles—some without homogeneous analogues—for performance and selectivity optimization. These handles include nanoparticle size, pore profile of porous supports, surface ligands and interface with oxide supports, and flow rate through a solid catalyst bed. Despite these available handles, however, conventional heterogeneous catalysts are themselves often structurally heterogeneous compared to homogeneous catalysts, which complicates efforts to optimizemore » and expand the scope of their reactivity and selectivity. Ongoing efforts in our laboratories are aimed to address the above challenge by heterogenizing homogeneous catalysts, which can be defined as the modification of homogeneous catalysts to render them in a separable (solid) phase from the starting materials and products. Specifically, we grow the small nanoclusters in dendrimers, a class of uniform polymers with the connectivity of fractal trees and generally radial symmetry. Thanks to their dense multivalency, shape persistence, and structural uniformity, dendrimers have proven to be versatile scaffolds for the synthesis and stabilization of small nanoclusters. Then these dendrimer-encapsulated metal clusters (DEMCs) are adsorbed onto mesoporous silica. Through this method, we have achieved selective transformations that had been challenging to accomplish in a heterogeneous setting, e.g., π-bond activation and aldol reactions. Extensive investigation into the catalytic systems under reaction conditions allowed us to correlate the structural features (e.g., oxidation states) of the catalysts and their activity. Moreover, we have demonstrated that supported DEMCs are also excellent catalysts for typical heterogeneous reactions, including hydrogenation and alkane isomerization. Critically, these investigations also confirmed that the supported DEMCs are heterogeneous and stable against leaching. Catalysts optimization is achieved through the modulation of various parameters. The clusters are oxidized (e.g., with PhICl 2) or reduced (e.g., with H 2) in situ. Changing the dendrimer properties (e.g., generation, terminal functional groups) is analogous to ligand modification in homogeneous catalysts, which affect both catalytic activity and selectivity. Similarly, pore size of the support is another factor in determining product distribution. In a flow reactor, the flow rate is adjusted to control the residence time of the starting material and intermediates, and thus the final product selectivity. Our approach to heterogeneous catalysis affords various advantages: (1) the catalyst system can tap into the reactivity typical to homogeneous catalysts, which conventional heterogeneous catalysts could not achieve; (2) unlike most homogeneous catalysts with comparable performance, the heterogenized homogeneous catalysts can be recycled; (3) improved activity or selectivity compared to conventional homogeneous catalysts is possible because of uniquely heterogeneous parameters for optimization. Here in this Account, we will briefly introduce metal clusters and describe the synthesis and characterizations of supported DEMCs. We will present the catalysis studies of supported DEMCs in both the batch and flow modes. Lastly, we will summarize the current state of heterogenizing homogeneous catalysis and provide future directions for this area of research.« less

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

Ye, Rong; Zhukhovitskiy, Aleksandr V.; Deraedt, Christophe V.

Recyclable catalysts, especially those that display selective reactivity, are vital for the development of sustainable chemical processes. Among available catalyst platforms, heterogeneous catalysts are particularly well-disposed toward separation from the reaction mixture via filtration methods, which renders them readily recyclable. Furthermore, heterogeneous catalysts offer numerous handles—some without homogeneous analogues—for performance and selectivity optimization. These handles include nanoparticle size, pore profile of porous supports, surface ligands and interface with oxide supports, and flow rate through a solid catalyst bed. Despite these available handles, however, conventional heterogeneous catalysts are themselves often structurally heterogeneous compared to homogeneous catalysts, which complicates efforts to optimizemore » and expand the scope of their reactivity and selectivity. Ongoing efforts in our laboratories are aimed to address the above challenge by heterogenizing homogeneous catalysts, which can be defined as the modification of homogeneous catalysts to render them in a separable (solid) phase from the starting materials and products. Specifically, we grow the small nanoclusters in dendrimers, a class of uniform polymers with the connectivity of fractal trees and generally radial symmetry. Thanks to their dense multivalency, shape persistence, and structural uniformity, dendrimers have proven to be versatile scaffolds for the synthesis and stabilization of small nanoclusters. Then these dendrimer-encapsulated metal clusters (DEMCs) are adsorbed onto mesoporous silica. Through this method, we have achieved selective transformations that had been challenging to accomplish in a heterogeneous setting, e.g., π-bond activation and aldol reactions. Extensive investigation into the catalytic systems under reaction conditions allowed us to correlate the structural features (e.g., oxidation states) of the catalysts and their activity. Moreover, we have demonstrated that supported DEMCs are also excellent catalysts for typical heterogeneous reactions, including hydrogenation and alkane isomerization. Critically, these investigations also confirmed that the supported DEMCs are heterogeneous and stable against leaching. Catalysts optimization is achieved through the modulation of various parameters. The clusters are oxidized (e.g., with PhICl 2) or reduced (e.g., with H 2) in situ. Changing the dendrimer properties (e.g., generation, terminal functional groups) is analogous to ligand modification in homogeneous catalysts, which affect both catalytic activity and selectivity. Similarly, pore size of the support is another factor in determining product distribution. In a flow reactor, the flow rate is adjusted to control the residence time of the starting material and intermediates, and thus the final product selectivity. Our approach to heterogeneous catalysis affords various advantages: (1) the catalyst system can tap into the reactivity typical to homogeneous catalysts, which conventional heterogeneous catalysts could not achieve; (2) unlike most homogeneous catalysts with comparable performance, the heterogenized homogeneous catalysts can be recycled; (3) improved activity or selectivity compared to conventional homogeneous catalysts is possible because of uniquely heterogeneous parameters for optimization. Here in this Account, we will briefly introduce metal clusters and describe the synthesis and characterizations of supported DEMCs. We will present the catalysis studies of supported DEMCs in both the batch and flow modes. Lastly, we will summarize the current state of heterogenizing homogeneous catalysis and provide future directions for this area of research.« less

Computer simulation of ledge formation and ledge interaction for the silicon (111) free surface

NASA Technical Reports Server (NTRS)

Balamane, H.; Halicioglu, T.; Tiller, W. A.

1987-01-01

Both strip and triangular clusters, composed of 2 -1 -1 line ledges, have been simulated on the Si (111) surface. The long-range ledge-ledge interaction and the surface stress tensor distribution have been evaluated for these two pill-box geometries using a semiempirical potential-energy function that incorporates both two-body and three-body contributions. The consequences of the ledge-ledge interaction on two-dimensional nucleation for Si (111) has been evaluated as a function of Si adatom supersaturation and shown to differ significantly from conventional theory, where such interaction is neglected.

Bottom-up meets top-down: tailored raspberry-like Fe3O4-Pt nanocrystal superlattices.

PubMed

Qiu, Fen; Vervuurt, René H J; Verheijen, Marcel A; Zaia, Edmond W; Creel, Erin B; Kim, Youngsang; Urban, Jeffrey J; Bol, Ageeth A

2018-03-29

Supported catalysts are widely used in industry and can be optimized by tuning the composition, chemical structure, and interface of the nanoparticle catalyst and oxide support. Here we firstly combine a bottom up colloidal synthesis method with a top down atomic layer deposition (ALD) process to achieve a raspberry-like Pt-decorated Fe3O4 (Fe3O4-Pt) nanoparticle superlattices. This nanocomposite ensures the precision of the catalyst/support interface, improving the catalytic efficiency of the Fe3O4-Pt nanocomposite system. The morphology of the hybrid nanocomposites resulting from different cycles of ALD was monitored by scanning transmission electron microscopy, giving insight into the nucleation and growth mechanism of the ALD process. X-ray photoelectron spectroscopy studies confirm the anticipated electron transfer from Fe3O4 to Pt through the nanocomposite interface. Photocurrent measurement further suggests that Fe3O4 superlattices with controlled decoration of Pt have substantial promise for energy-efficient photoelectrocatalytic oxygen evolution reaction. This work opens a new avenue for designing supported catalyst architectures via precisely controlled decoration of single component superlattices with noble metals.

Directing Reaction Pathways through Controlled Reactant Binding at Pd-TiO2 Interfaces.

PubMed

Zhang, Jing; Wang, Bingwen; Nikolla, Eranda; Medlin, J Will

2017-06-01

Recent efforts to design selective catalysts for multi-step reactions, such as hydrodeoxygenation (HDO), have emphasized the preparation of active sites at the interface between two materials having different properties. However, achieving precise control over interfacial properties, and thus reaction selectivity, has remained a challenge. Here, we encapsulated Pd nanoparticles (NPs) with TiO 2 films of regulated porosity to gain a new level of control over catalyst performance, resulting in essentially 100 % HDO selectivity for two biomass-derived alcohols. This catalyst also showed exceptional reaction specificity in HDO of furfural and m-cresol. In addition to improving HDO activity by maximizing the interfacial contact between the metal and metal oxide sites, encapsulation by the nanoporous oxide film provided a significant selectivity boost by restricting the accessible conformations of aromatics on the surface. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quaternary Basalts in Grand Canyon: Correlation of Flows Using Lidar, 40Ar/39Ar Dating, Geochemical Correlation, Neotectonic Studies, and History of Lava Dams

NASA Astrophysics Data System (ADS)

Crow, R. S.; Karlstrom, K. E.; McIntosh, W. C.; Dunbar, N. W.; Peters, L.; Raucci, J.; Umhoefer, P. J.

2005-12-01

In western Grand Canyon, basalts flowed into the already existing canyon from at least 719 ka to present. These basalts provide a key for deciphering Quaternary rates of incision, neotectonic slip rates on the Toroweap and Hurricane faults, and the history of lava dams. Stratigraphy and/or inset relationships between basalt flows is exceedingly complex because of the multiple eruptions, extreme topography, long transport distance, and incomplete preservation. Correlation of flows using 40Ar/39Ar dating, LIDAR data, orthophotography, and geochemical analysis, as well as structural and geomorphic studies, lead to a working hypothesis for four major episodes of basaltic eruptive activity. From 719 to 484 Ma major volcanoes erupted near the Toroweap fault zone. The extent of the remnants and presence of 527 ka dikes indicates that cones where built within Grand Canyon during this phase. These flows had the longest outflow (719 ka flow at mile 246). At 349 to 296 ka flows seem to have entered the canyon at Whitmore Wash, north rim. The two remaining episodes, dated at 199-193 ka and 109-97 ka are interpreted to have cascaded into the canyon at and upstream from Whitmore Wash. LIDAR/orthophotography interpretation of the tops and bottoms of the flows and geochemical analysis of phenocrysts aid in correlation of undated remnants and reconstructing the shape of volcanic edifices. Flows dated from 720-450 ka include Prospect, Black Ledge, D-Dam, and Toroweap flows, thus Black Ledge flows are considerably older than previously thought. The 350 to 300 flows include Whitmore, Layered Diabase, Massive Diabase, and 177-mile flows. All the dated 200 and 100 ka flows have been called Grey Ledge flows, suggesting that the Grey Ledge represents two distinct events. Basalt data indicate an interaction of canyon incision and Quaternary fault slip. Bedrock incision rates are calculated using dated flows that overly bedrock straths. Rates vary across active faults indicating fault dampening of apparent river incision rates. Incision rates for eastern Grand Canyon are 127 m/my over 387 ka. Similar rates just east of the Toroweap faults (136 m/my over 349 ka and 153 m/my over 484 ka) suggest that a fairly uniform regional rate of ~ 140 m/my can be considered the average rate for Grand Canyon incision east of the Toroweap fault. This is subequal to the sum of apparent incision rate just below the Toroweap fault (56 m/my over 484 ka) plus fault slip rate (90 m/my over 550 ka). Similarly, apparent incision rates below the Hurricane fault (66 m/my over 527 ka and 76 m/my over 604 ka, near Granite Park) plus fault slip rate (~80±20 m/my over 185 ka) is subequal to the far field incision rate. Accumulating data suggests that apparent incision rates are lowest adjacent to faults in the hanging wall and highest adjacent to faults in the footwall, with rates varying systematically across fault blocks. This suggests that faulting is taking place by domino rotation of blocks bounded by normal faults with mild listric character. These new empirical data help constrain physical models for Quaternary fault slip across the active Colorado Plateau- Basin and Range bounding structures.

Revealing the semiconductor–catalyst interface in buried platinum black silicon photocathodes

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

Aguiar, Jeffery A.; Anderson, Nicholas C.; Neale, Nathan R.

2016-01-01

Nanoporous 'black' silicon semiconductors interfaced with buried platinum nanoparticle catalysts have exhibited stable activity for photoelectrochemical hydrogen evolution even after months of exposure to ambient conditions. The mechanism behind this stability has not been explained in detail, but is thought to involve a Pt/Si interface free from SiOx layer that would adversely affect interfacial charge transfer kinetics. In this paper, we resolve the chemical composition and structure of buried Pt/Si interfaces in black silicon photocathodes from a micron to sub-nanometer level using aberration corrected analytical scanning transmission electron microscopy. Through a controlled electrodeposition of copper on samples aged for onemore » month in ambient conditions, we demonstrate that the main active catalytic sites are the buried Pt nanoparticles located below the 400-800 nm thick nanoporous SiOx layer. Though hydrogen production performance degrades over 100 h under photoelectrochemical operating conditions, this burying strategy preserves an atomically clean catalyst/Si interface free of oxide or other phases under air exposure and provides an example of a potential method for stabilizing silicon photoelectrodes from oxidative degradation in photoelectrochemical applications.« less

Atomistics of vapour–liquid–solid nanowire growth

PubMed Central

Wang, Hailong; Zepeda-Ruiz, Luis A.; Gilmer, George H.; Upmanyu, Moneesh

2013-01-01

Vapour–liquid–solid route and its variants are routinely used for scalable synthesis of semiconducting nanowires, yet the fundamental growth processes remain unknown. Here we employ atomic-scale computations based on model potentials to study the stability and growth of gold-catalysed silicon nanowires. Equilibrium studies uncover segregation at the solid-like surface of the catalyst particle, a liquid AuSi droplet, and a silicon-rich droplet–nanowire interface enveloped by heterogeneous truncating facets. Supersaturation of the droplets leads to rapid one-dimensional growth on the truncating facets and much slower nucleation-controlled two-dimensional growth on the main facet. Surface diffusion is suppressed and the excess Si flux occurs through the droplet bulk which, together with the Si-rich interface and contact line, lowers the nucleation barrier on the main facet. The ensuing step flow is modified by Au diffusion away from the step edges. Our study highlights key interfacial characteristics for morphological and compositional control of semiconducting nanowire arrays. PMID:23752586

Enhancing the Photocatalytic Hydrogen Evolution Performance of a Metal/Semiconductor Catalyst through Modulation of the Schottky Barrier Height by Controlling the Orientation of the Interface.

PubMed

Liu, Yang; Gu, Xin; Qi, Wen; Zhu, Hong; Shan, Hao; Chen, Wenlong; Tao, Peng; Song, Chengyi; Shang, Wen; Deng, Tao; Wu, Jianbo

2017-04-12

Construction of a metal-semiconductor heterojunction is a promising method to improve heterogeneous photocatalysis for various reactions. Although the structure and photocatalytic performance of such a catalyst system have been extensively studied, few reports have demonstrated the effect of interface orientation at the metal-semiconductor junction on junction-barrier bending and the electronic transport properties. Here, we construct a Pt/PbS heterojunction, in which Pt nanoparticles are used as highly active catalysts and PbS nanocrystals (NCs) with well-controlled shapes are used as light-harvesting supports. Experimental results show that the photoelectrocatalytic activities of the Pt/PbS catalyst are strongly dependent on the contacting facets of PbS at the junction. Pt/octahedral PbS NCs with exposed PbS(111) facets show the highest photoinduced enhancement of hydrogen evolution reaction activity, which is ∼14.38 times higher than that of the ones with only PbS(100) facets (Pt/cubic PbS NCs). This enhancement can further be rationalized by the different energy barriers of the Pt/PbS Schottky junction due to the specific band structure and electron affinity, which is also confirmed by the calculations based on density functional theory. Therefore, controlling the contacting interfaces of a metal/semiconductor material may offer an effective approach to form the desired heterojunction for optimization of the catalytic performance.

Phenomenological analysis of densification mechanism during spark plasma sintering of MgAl2O4

NASA Astrophysics Data System (ADS)

Bernard-Granger, Guillaume; Benameur, Nassira; Addad, Ahmed; Nygren, Mats; Guizard, Christian; Deville, Sylvain

2009-05-01

Spark plasma sintering (SPS) of MgAl2O4 powder was investigated at temperatures between 1200 and 1300{\\deg}C. A significant grain growth was observed during densification. The densification rate always exhibits at least one strong minimum, and resumes after an incubation period. Transmission electron microscopy investigations performed on sintered samples never revealed extensive dislocation activity in the elemental grains. The densification mechanism involved during SPS was determined by anisothermal (investigation of the heating stage of a SPS run) and isothermal methods (investigation at given soak temperatures). Grain-boundary sliding, accommodated by an in-series {interface-reaction/lattice diffusion of the O$^2$-anions} mechanism controlled by the interface-reaction step, governs densification. The zero-densification-rate period, detected for all soak temperatures, arise from the difficulty of annealing vacancies, necessary for the densification to proceed. The detection of atomic ledges at grain boundaries and the modification of the stoichiometry of spinel during SPS could be related to the difficulty to anneal vacancies at temperature soaks.

Near sulfur L-edge X-ray absorption spectra of methanethiol in isolation and adsorbed on a Au(111) surface: a theoretical study using the four-component static exchange approximation.

PubMed

Villaume, Sebastien; Ekström, Ulf; Ottosson, Henrik; Norman, Patrick

2010-06-07

The relativistic four-component static exchange approach for calculation of near-edge X-ray absorption spectra has been reviewed. Application of the method is made to the Au(111) interface and the adsorption of methanethiol by a study of the near sulfur L-edge spectrum. The binding energies of the sulfur 2p(1/2) and 2p(3/2) sublevels in methanethiol are determined to be split by 1.2 eV due to spin-orbit coupling, and the binding energy of the 2p(3/2) shell is lowered from 169.2 eV for the isolated system to 167.4 and 166.7-166.8 eV for methanethiol in mono- and di-coordinated adsorption sites, respectively (with reference to vacuum). In the near L-edge X-ray absorption fine structure spectrum only the sigma*(S-C) peak at 166 eV remains intact by surface adsorption, whereas transitions of predominantly Rydberg character are largely quenched in the surface spectra. The sigma*(S-H) peak of methanethiol is replaced by low-lying, isolated, sigma*(S-Au) peak(s), where the number of peaks in the latter category and their splittings are characteristic of the local bonding situation of the sulfur.

A Tandem Catalyst with Multiple Metal Oxide Interfaces Produced by Atomic Layer Deposition.

PubMed

Ge, Huibin; Zhang, Bin; Gu, Xiaomin; Liang, Haojie; Yang, Huimin; Gao, Zhe; Wang, Jianguo; Qin, Yong

2016-06-13

Ideal heterogeneous tandem catalysts necessitate the rational design and integration of collaborative active sites. Herein, we report on the synthesis of a new tandem catalyst with multiple metal-oxide interfaces based on a tube-in-tube nanostructure using template-assisted atomic layer deposition, in which Ni nanoparticles are supported on the outer surface of the inner Al2 O3 nanotube (Ni/Al2 O3 interface) and Pt nanoparticles are attached to the inner surface of the outer TiO2 nanotube (Pt/TiO2 interface). The tandem catalyst shows remarkably high catalytic efficiency in nitrobenzene hydrogenation over Pt/TiO2 interface with hydrogen formed in situ by the decomposition of hydrazine hydrate over Ni/Al2 O3 interface. This can be ascribed to the synergy effect of the two interfaces and the confined nanospace favoring the instant transfer of intermediates. The tube-in-tube tandem catalyst with multiple metal-oxide interfaces represents a new concept for the design of highly efficient and multifunctional nanocatalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Integrated CO2 capture-fixation chemistry via interfacial ionic liquid catalyst in laminar gas/liquid flow

NASA Astrophysics Data System (ADS)

Vishwakarma, Niraj K.; Singh, Ajay K.; Hwang, Yoon-Ho; Ko, Dong-Hyeon; Kim, Jin-Oh; Babu, A. Giridhar; Kim, Dong-Pyo

2017-03-01

Simultaneous capture of carbon dioxide (CO2) and its utilization with subsequent work-up would significantly enhance the competitiveness of CO2-based sustainable chemistry over petroleum-based chemistry. Here we report an interfacial catalytic reaction platform for an integrated autonomous process of simultaneously capturing/fixing CO2 in gas-liquid laminar flow with subsequently providing a work-up step. The continuous-flow microreactor has built-in silicon nanowires (SiNWs) with immobilized ionic liquid catalysts on tips of cone-shaped nanowire bundles. Because of the superamphiphobic SiNWs, a stable gas-liquid interface maintains between liquid flow of organoamines in upper part and gas flow of CO2 in bottom part of channel. The intimate and direct contact of the binary reagents leads to enhanced mass transfer and facilitating reactions. The autonomous integrated platform produces and isolates 2-oxazolidinones and quinazolines-2,4(1H,3H)-diones with 81-97% yields under mild conditions. The platform would enable direct CO2 utilization to produce high-valued specialty chemicals from flue gases without pre-separation and work-up steps.

Integrated CO2 capture-fixation chemistry via interfacial ionic liquid catalyst in laminar gas/liquid flow.

PubMed

Vishwakarma, Niraj K; Singh, Ajay K; Hwang, Yoon-Ho; Ko, Dong-Hyeon; Kim, Jin-Oh; Babu, A Giridhar; Kim, Dong-Pyo

2017-03-06

Simultaneous capture of carbon dioxide (CO 2 ) and its utilization with subsequent work-up would significantly enhance the competitiveness of CO 2 -based sustainable chemistry over petroleum-based chemistry. Here we report an interfacial catalytic reaction platform for an integrated autonomous process of simultaneously capturing/fixing CO 2 in gas-liquid laminar flow with subsequently providing a work-up step. The continuous-flow microreactor has built-in silicon nanowires (SiNWs) with immobilized ionic liquid catalysts on tips of cone-shaped nanowire bundles. Because of the superamphiphobic SiNWs, a stable gas-liquid interface maintains between liquid flow of organoamines in upper part and gas flow of CO 2 in bottom part of channel. The intimate and direct contact of the binary reagents leads to enhanced mass transfer and facilitating reactions. The autonomous integrated platform produces and isolates 2-oxazolidinones and quinazolines-2,4(1H,3H)-diones with 81-97% yields under mild conditions. The platform would enable direct CO 2 utilization to produce high-valued specialty chemicals from flue gases without pre-separation and work-up steps.

Integrated CO2 capture-fixation chemistry via interfacial ionic liquid catalyst in laminar gas/liquid flow

PubMed Central

Vishwakarma, Niraj K.; Singh, Ajay K.; Hwang, Yoon-Ho; Ko, Dong-Hyeon; Kim, Jin-Oh; Babu, A. Giridhar; Kim, Dong-Pyo

2017-01-01

Simultaneous capture of carbon dioxide (CO2) and its utilization with subsequent work-up would significantly enhance the competitiveness of CO2-based sustainable chemistry over petroleum-based chemistry. Here we report an interfacial catalytic reaction platform for an integrated autonomous process of simultaneously capturing/fixing CO2 in gas–liquid laminar flow with subsequently providing a work-up step. The continuous-flow microreactor has built-in silicon nanowires (SiNWs) with immobilized ionic liquid catalysts on tips of cone-shaped nanowire bundles. Because of the superamphiphobic SiNWs, a stable gas–liquid interface maintains between liquid flow of organoamines in upper part and gas flow of CO2 in bottom part of channel. The intimate and direct contact of the binary reagents leads to enhanced mass transfer and facilitating reactions. The autonomous integrated platform produces and isolates 2-oxazolidinones and quinazolines-2,4(1H,3H)-diones with 81–97% yields under mild conditions. The platform would enable direct CO2 utilization to produce high-valued specialty chemicals from flue gases without pre-separation and work-up steps. PMID:28262667

Control over the branched structures of platinum nanocrystals for electrocatalytic applications.

PubMed

Ma, Liang; Wang, Chengming; Gong, Ming; Liao, Lingwen; Long, Ran; Wang, Jinguo; Wu, Di; Zhong, Wei; Kim, Moon J; Chen, Yanxia; Xie, Yi; Xiong, Yujie

2012-11-27

Structural control of branched nanocrystals allows tuning two parameters that are critical to their catalytic activity--the surface-to-volume ratio, and the number of atomic steps, ledges, and kinks on surface. In this work, we have developed a simple synthetic system that allows tailoring the numbers of branches in Pt nanocrystals by tuning the concentration of additional HCl. In the synthesis, HCl plays triple functions in tuning branched structures via oxidative etching: (i) the crystallinity of seeds and nanocrystals; (ii) the number of {111} or {100} faces provided for growth sites; (iii) the supply kinetics of freshly formed Pt atoms in solution. As a result, tunable Pt branched structures--tripods, tetrapods, hexapods, and octopods with identical chemical environment--can be rationally synthesized in a single system by simply altering the etching strength. The controllability in branched structures enables to reveal that their electrocatalytic performance can be optimized by constructing complex structures. Among various branched structures, Pt octopods exhibit particularly high activity in formic acid oxidation as compared with their counterparts and commercial Pt/C catalysts. It is anticipated that this work will open a door to design more complex nanostructures and to achieve specific functions for various applications.

Multiphase transport in polymer electrolyte membrane fuel cells

NASA Astrophysics Data System (ADS)

Gauthier, Eric D.

Polymer electrolyte membrane fuel cells (PEMFCs) enable efficient conversion of fuels to electricity. They have enormous potential due to the high energy density of the fuels they utilize (hydrogen or alcohols). Power density is a major limitation to wide-scale introduction of PEMFCs. Power density in hydrogen fuel cells is limited by accumulation of water in what is termed fuel cell `flooding.' Flooding may occur in either the gas diffusion layer (GDL) or within the flow channels of the bipolar plate. These components comprise the electrodes of the fuel cell and balance transport of reactants/products with electrical conductivity. This thesis explores the role of electrode materials in the fuel cell and examines the fundamental connection between material properties and multiphase transport processes. Water is generated at the cathode catalyst layer. As liquid water accumulates it will utilize the largest pores in the GDL to go from the catalyst layer to the flow channels. Water collects to large pores via lateral transport at the interface between the GDL and catalyst layer. We have shown that water may be collected in these large pores from several centimeters away, suggesting that we could engineer the GDL to control flooding with careful placement and distribution of large flow-directing pores. Once liquid water is in the flow channels it forms slugs that block gas flow. The slugs are pushed along the channel by a pressure gradient that is dependent on the material wettability. The permeable nature of the GDL also plays a major role in slug growth and allowing bypass of gas between adjacent channels. Direct methanol fuel cells (DMFCs) have analogous multiphase flow issues where carbon dioxide bubbles accumulate, `blinding' regions of the fuel cell. This problem is fundamentally similar to water management in hydrogen fuel cells but with a gas/liquid phase inversion. Gas bubbles move laterally through the porous GDL and emerge to form large bubbles within the flow channel. We have compared the role of GDL materials in liquid drop and gas bubble formation and movement within fuel cells.

Development of Molecular Catalysts to Bridge the Gap between Heterogeneous and Homogeneous Catalysts

NASA Astrophysics Data System (ADS)

Ye, Rong

Catalysts, heterogeneous, homogeneous, and enzymatic, are comprised of nanometer-sized inorganic and/or organic components. They share molecular factors including charge, coordination, interatomic distance, bonding, and orientation of catalytically active atoms. By controlling the governing catalytic components and molecular factors, catalytic processes of a multichannel and multiproduct nature could be run in all three catalytic platforms to create unique end-products. Unifying the fields of catalysis is the key to achieving the goal of 100% selectivity in catalysis. Recyclable catalysts, especially those that display selective reactivity, are vital for the development of sustainable chemical processes. Among available catalyst platforms, heterogeneous catalysts are particularly well-disposed toward separation from the reaction mixture via filtration methods, which renders them readily recyclable. Furthermore, heterogeneous catalysts offer numerous handles - some without homogeneous analogues - for performance and selectivity optimization. These handles include nanoparticle size, pore profile of porous supports, surface ligands and interface with oxide supports, and flow rate through a solid catalyst bed. Despite these available handles, however, conventional heterogeneous catalysts are themselves often structurally heterogeneous compared to homogeneous catalysts, which complicates efforts to optimize and expand the scope of their reactivity and selectivity. Ongoing efforts are aimed to address the above challenge by heterogenizing homogeneous catalysts, which can be defined as the modification of homogeneous catalysts to render them in a separable (solid) phase from the starting materials and products. Specifically, we grow the small nanoclusters in dendrimers, a class of uniform polymers with the connectivity of fractal trees and generally radial symmetry. Thanks to their dense multivalency, shape persistence and structural uniformity, dendrimers have proven to be versatile scaffolds for the synthesis and stabilization of small nanoclusters. Then these dendrimer-encapsulated metal clusters (DEMCs) are adsorbed onto mesoporous silica. Through this method, we have achieved selective transformations that had been challenging to accomplish in a heterogeneous setting, e.g. pi-bond activation and aldol reactions. Extensive investigation into the catalytic systems under reaction conditions allowed us to correlate the structural features (e.g. oxidation states) of the catalysts and their activity. Moreover, we have demonstrated that supported DEMCs are also excellent catalysts for typical heterogeneous reactions, including hydrogenation and alkane isomerization. Critically, these investigations also confirmed that the supported DEMCs are heterogeneous and stable against leaching. Catalysts optimization is achieved through the modulation of various parameters. The clusters are oxidized (e.g., with PhICl2) or reduced (e.g., with H2) in situ. Changing the dendrimer properties (e.g., generation, terminal functional groups) is analogous to ligand modification in homogeneous catalysts, which affect both catalytic activity and selectivity. Similarly, pore size of the support is another factor in determining product distribution. In a flow reactor, the flow rate is adjusted to control the residence time of the starting material and intermediates, and thus the final product selectivity. Our approach to heterogeneous catalysis affords various advantages: (1) the catalyst system can tap into the reactivity typical to homogeneous catalysts, which conventional heterogeneous catalysts could not achieve; (2) unlike most homogeneous catalysts with comparable performance, the heterogenized homogeneous catalysts can be recycled; (3) improved activity or selectivity compared to conventional homogeneous catalysts is possible because of uniquely heterogeneous parameters for optimization. While localized surface plasmon resonance (LSPR) provides a powerful platform for nanoparticle catalysis, our studies suggest that in some cases interband transitions should be considered as an alternative mechanism of light-driven nanoparticle catalysis. The benefits already demonstrated by plasmonic nanostructures as catalysts provided the impetus for examining complementary activation modes based on the metal nanoparticle itself. Leveraging these transitions has the potential to provide a means to highly active catalysis modes that would otherwise be challenging to access. For example, for the preparation of highly active metal catalysts on a subnanosized scale is challenging, thus limiting their exploitation and study in catalysis. Our work suggests a novel and facile strategy for the formation of highly active gold nanocluster catalysts by light illumination of the interband transitions in the presence of the appropriate substrate.

Design, development, and demonstration of a fully LabVIEW controlled in situ electrochemical Fourier transform infrared setup combined with a wall-jet electrode to investigate the electrochemical interface of nanoparticulate electrocatalysts under reaction conditions.

PubMed

Nesselberger, Markus; Ashton, Sean J; Wiberg, Gustav K H; Arenz, Matthias

2013-07-01

We present a detailed description of the construction of an in situ electrochemical ATR-FTIR setup combined with a wall-jet electrode to investigate the electrocatalytic properties of nanoparticulate catalysts in situ under controlled mass transport conditions. The presented setup allows the electrochemical interface to be probed in combination with the simultaneous determination of reaction rates. At the same time, the high level of automation allows it to be used as a standard tool in electrocatalysis research. The performance of the setup was demonstrated by probing the oxygen reduction reaction on a platinum black catalyst in sulfuric electrolyte.

Systems and methods for controlling diesel engine emissions

DOEpatents

Webb, Cynthia Chaffin; Weber, Phillip Anthony; Khair, Magdi K.

2004-06-01

Systems and methods for controlling diesel engine emissions, including, for example, oxides of nitrogen emissions, particulate matter emissions, and the like. The emission control system according to this invention is provided in the exhaust passageway of a diesel engine and includes a catalyst-based particulate filter; and first and second lean NO.sub.x trap systems coupled to the catalyst-based particulate filter. The first and second lean NO.sub.x trap systems are arranged in a parallel flow configuration with each other. Each of the first and second lean NO.sub.x trap systems include a carbon monoxide generating catalyst device, a sulfur trap device, a lean NO.sub.x device, a supplemental fuel injector device, and a plurality of flow diverter devices.

Correlating Oxygen Evolution Catalysts Activity and Electronic Structure by a High-Throughput Investigation of Ni1-y-zFeyCrzOx

PubMed Central

Schwanke, Christoph; Stein, Helge Sören; Xi, Lifei; Sliozberg, Kirill; Schuhmann, Wolfgang; Ludwig, Alfred; Lange, Kathrin M.

2017-01-01

High-throughput characterization by soft X-ray absorption spectroscopy (XAS) and electrochemical characterization is used to establish a correlation between electronic structure and catalytic activity of oxygen evolution reaction (OER) catalysts. As a model system a quasi-ternary materials library of Ni1-y-zFeyCrzOx was synthesized by combinatorial reactive magnetron sputtering, characterized by XAS, and an automated scanning droplet cell. The presence of Cr was found to increase the OER activity in the investigated compositional range. The electronic structure of NiII and CrIII remains unchanged over the investigated composition spread. At the Fe L-edge a linear combination of two spectra was observed. These spectra were assigned to FeIII in Oh symmetry and FeIII in Td symmetry. The ratio of FeIII Oh to FeIII Td increases with the amount of Cr and a correlation between the presence of the FeIII Oh and a high OER activity is found. PMID:28287134

Correlating Oxygen Evolution Catalysts Activity and Electronic Structure by a High-Throughput Investigation of Ni1-y-zFeyCrzOx

NASA Astrophysics Data System (ADS)

Schwanke, Christoph; Stein, Helge Sören; Xi, Lifei; Sliozberg, Kirill; Schuhmann, Wolfgang; Ludwig, Alfred; Lange, Kathrin M.

2017-03-01

High-throughput characterization by soft X-ray absorption spectroscopy (XAS) and electrochemical characterization is used to establish a correlation between electronic structure and catalytic activity of oxygen evolution reaction (OER) catalysts. As a model system a quasi-ternary materials library of Ni1-y-zFeyCrzOx was synthesized by combinatorial reactive magnetron sputtering, characterized by XAS, and an automated scanning droplet cell. The presence of Cr was found to increase the OER activity in the investigated compositional range. The electronic structure of NiII and CrIII remains unchanged over the investigated composition spread. At the Fe L-edge a linear combination of two spectra was observed. These spectra were assigned to FeIII in Oh symmetry and FeIII in Td symmetry. The ratio of FeIII Oh to FeIII Td increases with the amount of Cr and a correlation between the presence of the FeIII Oh and a high OER activity is found.

Dramatically different kinetics and mechanism at solid/liquid and solid/gas interfaces for catalytic isopropanol oxidation over size-controlled platinum nanoparticles.

PubMed

Wang, Hailiang; Sapi, Andras; Thompson, Christopher M; Liu, Fudong; Zherebetskyy, Danylo; Krier, James M; Carl, Lindsay M; Cai, Xiaojun; Wang, Lin-Wang; Somorjai, Gabor A

2014-07-23

We synthesize platinum nanoparticles with controlled average sizes of 2, 4, 6, and 8 nm and use them as model catalysts to study isopropanol oxidation to acetone in both the liquid and gas phases at 60 °C. The reaction at the solid/liquid interface is 2 orders of magnitude slower than that at the solid/gas interface, while catalytic activity increases with the size of platinum nanoparticles for both the liquid-phase and gas-phase reactions. The activation energy of the gas-phase reaction decreases with the platinum nanoparticle size and is in general much higher than that of the liquid-phase reaction which is largely insensitive to the size of catalyst nanoparticles. Water substantially promotes isopropanol oxidation in the liquid phase. However, it inhibits the reaction in the gas phase. The kinetic results suggest different mechanisms between the liquid-phase and gas-phase reactions, correlating well with different orientations of IPA species at the solid/liquid interface vs the solid/gas interface as probed by sum frequency generation vibrational spectroscopy under reaction conditions and simulated by computational calculations.

Transmission electron microscopy investigation of interfaces in a two-phase TiAl alloy

NASA Astrophysics Data System (ADS)

Mahon, G. J.; Howe, J. M.

1990-06-01

The atomic structures of the γ/α2 and γ/γT interfaces in a TiAl alloy were investigated using conventional and high-resolution transmission electron microscopy (TEM) in order to understand the growth mechanisms and deformation behavior of the two-phase alloy. The results show that the α2 plates grow from the γ phase by the migration of a/6<112> partial dislocation ledges across the faces and that the γ/α2 interface usually contains closely spaced arrays of interfacial dislocations. Deformation twins cut through both γ twin boundaries and α2 plates during deformation, although slip of twinning c slocations through α2 appears to be a difficult process. Both the γ/α2 and γ/γT interfaces can be imaged and modeled at the atomic level, although slight crystal and/or beam tilt can complicate image interpretation.

Analysis of a gas-liquid film plasma reactor for organic compound oxidation.

PubMed

Hsieh, Kevin; Wang, Huijuan; Locke, Bruce R

2016-11-05

A pulsed electrical discharge plasma formed in a tubular reactor with flowing argon carrier gas and a liquid water film was analyzed using methylene blue as a liquid phase hydroxyl radical scavenger and simultaneous measurements of hydrogen peroxide formation. The effects of liquid flow rate, liquid conductivity, concentration of dye, and the addition of ferrous ion on dye decoloration and degradation were determined. Higher liquid flow rates and concentrations of dye resulted in less decoloration percentages and hydrogen peroxide formation due to initial liquid conductivity effects and lower residence times in the reactor. The highest decoloration energy yield of dye found in these studies was 5.2g/kWh when using the higher liquid flow rate and adding the catalyst. The non-homogeneous nature of the plasma discharge favors the production of hydrogen peroxide in the plasma-liquid interface over the chemical oxidation of the organic in the bulk liquid phase and post-plasma reactions with the Fenton catalyst lead to complete utilization of the plasma-formed hydrogen peroxide. Copyright © 2016 Elsevier B.V. All rights reserved.

Controlling the charge state of supported nanoparticles in catalysis: lessons from model systems.

PubMed

Pacchioni, Gianfranco; Freund, Hans-Joachim

2018-04-26

Model systems are very important to identify the working principles of real catalysts, and to develop concepts that can be used in the design of new catalytic materials. In this review we report examples of the use of model systems to better understand and control the occurrence of charge transfer at the interface between supported metal nanoparticles and oxide surfaces. In the first part of this article we concentrate on the nature of the support, and on the basic difference in metal/oxide bonding going from a wide-gap non-reducible oxide material to reducible oxide semiconductors. The roles of oxide nanostructuring, bulk and surface defectiveness, and doping with hetero-atoms are also addressed, as they are all aspects that severely affect the metal/oxide interaction. Particular attention is given to the experimental measures of the occurrence of charge transfer at the metal/oxide interface. In this respect, systems based on oxide ultrathin films are particularly important as they allow the use of scanning probe spectroscopies which, often in combination with other measurements and with first principles theoretical simulations, allow full characterization of small supported nanoparticles and their charge state. In a few selected cases, a precise count of the electrons transferred between the oxide and the supported nanoparticle has been possible. Charge transfer can occur through thin, two-dimensional oxide layers also thanks to their structural flexibility. The flow of charge through the oxide film and the formation of charged adsorbates are accompanied in fact by a substantial polaronic relaxation of the film surface which can be rationalized based on electrostatic arguments. In the final part of this review the relationships between model systems and real catalysts are addressed by discussing some examples of how lessons learned from model systems have helped in rationalizing the behavior of real catalysts under working conditions.

Tuning Selectivity of CO 2 Hydrogenation Reactions at the Metal/Oxide Interface

DOE PAGES

Kattel, Shyam; Liu, Ping; Chen, Jingguang G.

2017-06-26

The chemical transformation of CO 2 not only mitigates the anthropogenic CO 2 emission into the Earth’s atmosphere but also produces carbon compounds that can be used as precursors for the production of chemicals and fuels. The activation and conversion of CO 2 can be achieved on multifunctional catalytic sites available at the metal/oxide interface by taking advantage of the synergy between the metal nanoparticles and oxide support. In this paper, we look at the recent progress in mechanistic studies of CO 2 hydrogenation to C1 (CO, CH 3OH, and CH 4) compounds on metal/oxide catalysts. On this basis, wemore » are able to provide a better understanding of the complex reaction network, grasp the capability of manipulating structure and combination of metal and oxide at the interface in tuning selectivity, and identify the key descriptors to control the activity and, in particular, the selectivity of catalysts. In conclusion, we also discuss challenges and future research opportunities for tuning the selective conversion of CO 2 on metal/oxide catalysts.« less

Rotating shielded crane system

DOEpatents

Commander, John C.

1988-01-01

A rotating, radiation shielded crane system for use in a high radiation test cell, comprises a radiation shielding wall, a cylindrical ceiling made of radiation shielding material and a rotatable crane disposed above the ceiling. The ceiling rests on an annular ledge intergrally attached to the inner surface of the shielding wall. Removable plugs in the ceiling provide access for the crane from the top of the ceiling into the test cell. A seal is provided at the interface between the inner surface of the shielding wall and the ceiling.

Kyanite-Bearing Migmatites at Ledge Mountain, Adirondack Highlands

NASA Astrophysics Data System (ADS)

Swanson, B.; Leech, M.; Metzger, E. P.

2017-12-01

Sillimanite-rich felsic migmatites exposed at Ledge Mountain represent the only location in the Adirondack Highlands where kyanite has been found. The texturally young kyanite is overprinted on sillimanite in largely undeformed pegmatitic leucosomes, suggesting a late episode of melting taking place deeper than previously thought, and requiring a counter-clockwise P-T path. A final phase of anatexis ca. 1050 Ma in the Eastern Adirondack Highlands is consistent with an influx of fluid or decompression from extension in sillimanite-bearing migmatites. Temperatures both from this study and previous work are consistent with granulite-facies metamorphism, however the presence of kyanite requires higher pressure conditions corresponding to deeper burial of these central Adirondack rocks. We used Perple_X to model phase equilibria using XRF+ICP-MS whole-rock chemistries for the kyanite-bearing migmatites. Pseudosection models suggest that the peak P-T mineral assemblage kyanite + mesoperthite + garnet + rutile formed at approximately 15-20kb and 1000°C which is higher than previously proposed for granulites in the region. These P-T conditions for peak metamorphism are similar to those reported for the distinctive and relatively rare assemblage that we observe kyanite + hypersolvus feldspar (now mesoperthite) + garnet + rutile. We have evidence of isothermal decompression to <11kb and 880°-1000°C based on Grt + Pl equilibrium in the assemblage Grt + Pl ± Kfs + Qz + Ilm + melt. The leucocratic melt phase comprises 16 vol. % of the rock at these P-T conditions which is sufficient for ductile flow in the deep crust. This melt phase is present syn-exhumation and helped to buoyantly exhume Ledge Moutain rocks beneath bounding normal faults as a granitic gneiss dome. Preliminary U-Pb SHRIMP zircon ages from Ledge Mountain kyanite-bearing migmatites show anatexis continuing well after high-grade metamorphism is believed to have ceased in the range. A counter-clockwise P-T path is consistent with the mechanisms in the current model, and this study indicates anatectic melting persisted into the Rigolet phase. The Ledge Mountain migmatite may represent the Hawkeye granite and/or Lyon Mountain Gneiss that were metamorphosed to sillimanite grade and then overprinted by a higher pressure, lower temperature assemblage.

Novel electrospun gas diffusion layers for polymer electrolyte membrane fuel cells: Part II. In operando synchrotron imaging for microscale liquid water transport characterization

NASA Astrophysics Data System (ADS)

Chevalier, S.; Ge, N.; Lee, J.; George, M. G.; Liu, H.; Shrestha, P.; Muirhead, D.; Lavielle, N.; Hatton, B. D.; Bazylak, A.

2017-06-01

This is the second paper in a two-part series in which we investigate the impact of the gas diffusion layer structure on the liquid water distribution in an operating polymer electrolyte membrane (PEM) fuel cell through the procedures of design, fabrication, and testing of novel hydrophobic electrospun gas diffusion layers (eGDLs). In this work, fibre diameters and alignment in eGDLs are precisely controlled, and concurrent synchrotron X-ray radiography and electrochemical impedance spectroscopy (EIS) are used to evaluate the influence of the controlled eGDL parameters on the liquid water distribution and on membrane liquid water content. For eGDLs with small fibre diameters (150-200 nm) and correspondingly smaller pore sizes, reduced liquid water accumulation under the flow field ribs is observed. However, more liquid water is pinned onto the eGDL - at the interface with flow field channels. Orienting fibre alignment perpendicular to the flow field channel direction leads to improved eGDL-catalyst layer contact and prevents rib-channel membrane deformation. On the other hand, eGDLs facilitate significant membrane dry-out, even under highly humidified operating conditions at high current densities.

Catalytic dehydrogenation of amine borane complexes

NASA Technical Reports Server (NTRS)

Mohajeri, Nahid (Inventor); Tabatabaie-Raissi, Ali (Inventor)

2007-01-01

A method of generating hydrogen includes the steps of providing an amine borane (AB) complex, at least one hydrogen generation catalyst, and a solvent, and mixing these components. Hydrogen is generated. The hydrogen produced is high purity hydrogen suitable for PEM fuel cells. A hydrolytic in-situ hydrogen generator includes a first compartment that contains an amine borane (AB) complex, a second container including at least one hydrogen generation catalyst, wherein the first or second compartment includes water or other hydroxyl group containing solvent. A connecting network permits mixing contents in the first compartment with contents in the second compartment, wherein high purity hydrogen is generated upon mixing. At least one flow controller is provided for controlling a flow rate of the catalyst or AB complex.

Catalytic dehydrogenation of amine borane complexes

NASA Technical Reports Server (NTRS)

Tabatabaie-Raissi, Ali (Inventor); Mohajeri, Nahid (Inventor); Bokerman, Gary (Inventor)

2009-01-01

A method of generating hydrogen includes the steps of providing an amine borane (AB) complex, at least one hydrogen generation catalyst, and a solvent, and mixing these components Hydrogen is generated. The hydrogen produced is high purity hydrogen suitable for PEM fuel cells. A hydrolytic in-situ hydrogen generator includes a first compartment that contains an amine borane (AB) complex, a second container including at least one hydrogen generation catalyst, wherein the first or second compartment includes water or other hydroxyl group containing solvent. A connecting network permits mixing contents in the first compartment with contents in the second compartment, wherein high purity hydrogen is generated upon mixing. At least one flow controller is provided for controlling a flow rate of the catalyst or AB complex.

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

27 CFR 9.224 - Wisconsin Ledge.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2013-04-01 2013-04-01 false Wisconsin Ledge. 9.224... Wisconsin Ledge. (a) Name. The name of the viticultural area described in this section is “Wisconsin Ledge”. For purposes of part 4 of this chapter, “Wisconsin Ledge” is a term of viticultural significance. (b...

27 CFR 9.224 - Wisconsin Ledge.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2014-04-01 2014-04-01 false Wisconsin Ledge. 9.224... Wisconsin Ledge. (a) Name. The name of the viticultural area described in this section is “Wisconsin Ledge”. For purposes of part 4 of this chapter, “Wisconsin Ledge” is a term of viticultural significance. (b...

27 CFR 9.224 - Wisconsin Ledge.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2012-04-01 2012-04-01 false Wisconsin Ledge. 9.224... Wisconsin Ledge. (a) Name. The name of the viticultural area described in this section is “Wisconsin Ledge”. For purposes of part 4 of this chapter, “Wisconsin Ledge” is a term of viticultural significance. (b...

Bimetallic Pt-Au Nanocatalysts on ZnO/Al2O3/Monolith for Air Pollution Control.

PubMed

Kim, Ki-Joong; Ahn, Ho-Geun

2015-08-01

The catalytic activity of a monolithic catalyst with nanosized Pt and Au particles on ZnO/Al2O3 (Pt-Au/ZnO/Al2O3/M) prepared by a wash-coat method was examined, specifically for toluene oxidation. Scanning electron microscopy image showed clearly the formation of a ZnO/Al2O3 layer on the monolith. Nanosized Pt-Au particles on ZnO/Al2O3/M with different sizes could be found in the Pt-Au/ZnO/Al2O3/M catalyst. The conversion of toluene decreased with increasing toluene concentration and was also largely affected by the feed flow rate. The Pt-Au/ZnO/Al2O3/M catalysts prepared in this work have almost the same activity (molecules of toluene per second) compared with a powder Pt-Au/ZnO/Al2O3 catalyst with the same loadings of Pt and Au components; thus this catalyst could be used in controlling air pollution with very low concentrations and high flow rate.

Polymer-based chromophore-catalyst assemblies for solar energy conversion

NASA Astrophysics Data System (ADS)

Leem, Gyu; Sherman, Benjamin D.; Schanze, Kirk S.

2017-12-01

The synthesis of polymer-based assemblies for light harvesting has been motivated by the multi-chromophore antennas that play a role in natural photosynthesis for the potential use in solar conversion technologies. This review describes a general strategy for using polymer-based chromophore-catalyst assemblies for solar-driven water oxidation at a photoanode in a dye-sensitized photoelectrochemical cell (DSPEC). This report begins with a summary of the synthetic methods and fundamental photophysical studies of light harvesting polychormophores in solution which show these materials can transport excited state energy to an acceptor where charge-separation can occur. In addition, studies describing light harvesting polychromophores containing an anchoring moiety (ionic carboxylate) for covalent bounding to wide band gap mesoporous semiconductor surfaces are summarized to understand the photophysical mechanisms of directional energy flow at the interface. Finally, the performance of polychromophore/catalyst assembly-based photoanodes capable of light-driven water splitting to oxygen and hydrogen in a DSPEC are summarized.

Polymer-based chromophore-catalyst assemblies for solar energy conversion.

PubMed

Leem, Gyu; Sherman, Benjamin D; Schanze, Kirk S

2017-01-01

The synthesis of polymer-based assemblies for light harvesting has been motivated by the multi-chromophore antennas that play a role in natural photosynthesis for the potential use in solar conversion technologies. This review describes a general strategy for using polymer-based chromophore-catalyst assemblies for solar-driven water oxidation at a photoanode in a dye-sensitized photoelectrochemical cell (DSPEC). This report begins with a summary of the synthetic methods and fundamental photophysical studies of light harvesting polychormophores in solution which show these materials can transport excited state energy to an acceptor where charge-separation can occur. In addition, studies describing light harvesting polychromophores containing an anchoring moiety (ionic carboxylate) for covalent bounding to wide band gap mesoporous semiconductor surfaces are summarized to understand the photophysical mechanisms of directional energy flow at the interface. Finally, the performance of polychromophore/catalyst assembly-based photoanodes capable of light-driven water splitting to oxygen and hydrogen in a DSPEC are summarized.

Soft X-ray spectroscopy of transition metal compounds: a theoretical perspective

NASA Astrophysics Data System (ADS)

Bokarev, S. I.; Hilal, R.; Aziz, S. G.; Kühn, O.

2017-01-01

To date, X-ray spectroscopy has become a routine tool that can reveal highly local and element-specific information on the electronic structure of atoms in complex environments. Here, we report on the development of an efficient and versatile theoretical methodology for the treatment of soft X-ray spectra of transition metal compounds based on the multi-configurational self-consistent field electronic structure theory. A special focus is put on the L-edge photon-in/photon-out and photon-in/electron-out processes, i.e. X-ray absorption, resonant inelastic scattering, partial fluorescence yield, and photoelectron spectroscopy, all treated on the same theoretical footing. The investigated systems range from small prototypical coordination compounds and catalysts to aggregates of biomolecules.

Surface profile control of FeNiPt/Pt core/shell nanowires for oxygen reduction reaction

DOE PAGES

Zhu, Huiyuan; Zhang, Sen; Su, Dong; ...

2015-03-18

The ever-increasing energy demand requires renewable energy schemes with low environmental impacts. Electrochemical energy conversion devices, such as fuel cells, combine fuel oxidization and oxygen reduction reactions and have been studied extensively for renewable energy applications. However, their energy conversion efficiency is often limited by kinetically sluggish chemical conversion reactions, especially oxygen reduction reaction (ORR). [1-5] To date, extensive efforts have been put into developing efficient ORR catalysts with controls on catalyst sizes, compositions, shapes and structures. [6-12] Recently, Pt-based catalysts with core/shell and one-dimensional nanowire (NW) morphologies were found to be promising to further enhance ORR catalysis.more » With the core/shell structure, the ORR catalysis of a nanoparticle (NP) catalyst can be tuned by both electronic and geometric effects at the core/shell interface. [10,13,14] With the NW structure, the catalyst interaction with the conductive support can be enhanced to facilitate electron transfer between the support and the NW catalyst and to promote ORR. [11,15,16]« less

Investigation of the Alkaline Electrochemical Interface and Development of Composite Metal/Metal-Oxides for Hydrogen and Oxygen Electrodes

NASA Astrophysics Data System (ADS)

Bates, Michael

Understanding the fundamentals of electrochemical interfaces will undoubtedly reveal a path forward towards a society based on clean and renewable energy. In particular, it has been proposed that hydrogen can play a major role as an energy carrier of the future. To fully utilize the clean energy potential of a hydrogen economy, it is vital to produce hydrogen via water electrolysis, thus avoiding co-production of CO2 inherent to reformate hydrogen. While significant research efforts elsewhere are focused on photo-chemical hydrogen production from water, the inherent low efficiency of this method would require a massive land-use footprint to achieve sufficient hydrogen production rates to integrate hydrogen into energy markets. Thus, this research has primarily focused on the water splitting reactions on base-metal catalysts in the alkaline environment. Development of high-performance base-metal catalysts will help move alkaline water electrolysis to the forefront of hydrogen production methods, and when paired with solar and wind energy production, represents a clean and renewable energy economy. In addition to the water electrolysis reactions, research was conducted to understand the de-activation of reversible hydrogen electrodes in the corrosive environment of the hydrogen-bromine redox flow battery. Redox flow batteries represent a promising energy storage option to overcome the intermittency challenge of wind and solar energy production methods. Optimization of modular and scalable energy storage technology will allow higher penetration of renewable wind and solar energy into the grid. In Chapter 1, an overview of renewable energy production methods and energy storage options is presented. In addition, the fundamentals of electrochemical analysis and physical characterization of the catalysts are discussed. Chapter 2 reports the development of a Ni-Cr/C electrocatalyst with unprecedented mass-activity for the hydrogen evolution reaction (HER) in alkaline electrolyte. The HER kinetics of numerous binary & ternary Ni-alloys and composite Ni/metal-oxide/C samples were evaluated in aqueous 0.1 M KOH electrolyte. Furthermore a model of the double layer interface is proposed, which helps explain the observed ensemble effect in the presence of AEI. In Chapter 3, Ni-Fe and Ni-Fe-Co mixed-metal-oxide (MMO) films were investigated for oxygen evolution reaction (OER) activity in 0.1M KOH on high surface area Raney-Nickel supports. During investigations of MMO activity, aniline was identified as a useful "capping agent" for synthesis of high-surface area MMO-polyaniline (PANI) composite materials. A Ni-Fe-Co/PANI-Raney-Ni catalyst was developed which exhibits enhanced mass-activity compared to state-of-the-art Ni-Fe OER electrocatalysts reported to date. The morphology of the MMO catalyst film on PANI/Raney-Ni support provides excellent dispersion of active-sites and should maintain high active-site utilization for catalyst loading on gas-diffusion electrodes. In Chapter 4, the de-activation of reversible-hydrogen electrode catalysts was investigated and the development of a Pt-Ir-Nx/C catalyst is reported, which exhibits significantly increased stability in the HBr/Br 2 electrolyte. In contrast a Pt-Ir/C catalyst exhibited increased tolerance to high-voltage cycling and in particular showed recovery of electrocatalytic activity after reversible de-activation (presumably from bromide adsorption and subsequent oxidative bromide stripping). Under the harshest testing conditions of high-voltage cycling or exposure to Br2 the Pt-based catalyst showed a trend in stability: Pt < Pt-Ir < Pt-Ir-Nx. (Abstract shortened by UMI.).

Two dimensional, transient catalytic combustion of CO-air on platinum

NASA Technical Reports Server (NTRS)

Sinha, N.; Bruno, C.; Bracco, F. V.

1985-01-01

The light off transient of catalytic combustion of lean CO-air mixtures in a platinum coated channel of a honeycomb monolith is studied with a model that resolves transient radial and axial gradients in both the gas and the solid. For the conditions studied it is concluded that: the initial heat release occurs near the entrance at the gas-solid interface and is controlled by heterogeneous reactions; large spatial and temporal temperature gradients occur in the solid near the entrance controlled mostly by the availability of fuel; the temperature of the solid near the entrance achieves almost its steady state value before significant heating of the back; heterogeneous reactions and the gas heated up front and flowing downstream heat the back of the solid; the overall transient time is controlled by the thermal inertia of the solid and by forced convection; radiation significantly influences both transient and steady state particularly near the entrance; the oxidation of CO occurs mostly on the catalyst and becomes diffusion controlled soon into the transient.

High-throughput continuous flow synthesis of nickel nanoparticles for the catalytic hydrodeoxygenation of guaiacol

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

Roberts, Emily J.; Habas, Susan E.; Wang, Lu

2016-11-07

The translation of batch chemistries to high-throughput continuous flow methods dresses scaling, automation, and reproducibility concerns associated with the implementation of colloidally prepared nanoparticle (NP) catalysts for industrial catalytic processes. Nickel NPs were synthesized by the high-temperature amine reduction of a Ni2+ precursor using a continuous millifluidic (mF) flow method, achieving yields greater than 60%. The resulting Ni NP catalysts were compared against catalysts prepared in a batch reaction under conditions analogous to the continuous flow conditions with respect to total reaction volume, time, and temperature and by traditional incipient wetness (IW) impregnation for the hydrodeoxygenation (HDO) of guaiacol undermore » ex situ catalytic fast pyrolysis conditions. Compared to the IW method, the colloidally prepared NPs displayed increased morphological control and narrowed size distributions, and the NPs prepared by both methods showed similar size, shape, and crystallinity. The Ni NP catalyst synthesized by the continuous flow method exhibited similar H-adsorption site densities, site-time yields, and selectivities towards deoxygenated products as compared to the analogous batch reaction, and outperformed the IW catalyst with respect to higher selectivity to lower oxygen content products and a 6.9-fold slower deactivation rate. These results demonstrate the utility of synthesizing colloidal Ni NP catalysts using continuous flow methods while maintaining the catalytic properties displayed by the batch equivalent. Finally, this methodology can be extended to other catalytically relevant base metals for the high-throughput synthesis of metal NPs for the catalytic production of biofuels.« less

Engineering Pt/Pd Interfacial Electronic Structures for Highly Efficient Hydrogen Evolution and Alcohol Oxidation.

PubMed

Fan, Jinchang; Qi, Kun; Zhang, Lei; Zhang, Haiyan; Yu, Shansheng; Cui, Xiaoqiang

2017-05-31

Tailoring the interfacial structure of Pt-based catalysts has emerged as an effective strategy to improve catalytic activity. However, little attention has been focused on investigating the relationship between the interfacial facets and their catalytic activity. Here, we design and implement Pd-Pt interfaces with controlled heterostructure features by epitaxially growing Pt nanoparticles on Pd nanosheets. On the basis of both density functional theory calculation and experimental results, we demonstrate that charge transfer from Pd to Pt is highly dependent on the interfacial facets of Pd substrates. Therefore, the Pd-Pt heterostructure with Pd(100)-Pt interface exhibits excellent activity and long-term stability for hydrogen evolution and methanol/ethanol oxidation reactions in alkaline medium, much better than that with Pd (111)-Pt interface or commercial Pt/C. Interfacial crystal facet-dependent electronic structural modulation sheds a light on the design and investigation of new heterostructures for high-activity catalysts.

Installation for the catalytic afterburning of exhaust gases of a multi-cylinder internal combustion engine

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

Lange, K.

1974-04-24

An installation for the catalytic afterburning of exhaust gases of a multi-cylinder internal combustion engine has two cylinder rows with two exhaust gas lines, each of which includes at least one catalyst. A temperature-responsive control is operable during engine start-up to conduct substantially the entire exhaust gas flow from the internal combustion engine during warmup for a predetermined time by way of only one of the two catalyst and then, after a short period of time, to conduct the exhaust gas flow from each row of cylinders by way of its associated gas line and catalyst.

Model study on transesterification of soybean oil to biodiesel with methanol using solid base catalyst.

PubMed

Liu, Xuejun; Piao, Xianglan; Wang, Yujun; Zhu, Shenlin

2010-03-25

Modeling of the transesterification of vegetable oils to biodiesel using a solid base as a catalyst is very important because the mutual solubilities of oil and methanol will increase with the increasing biodiesel yield. The heterogeneous liquid-liquid-solid reaction system would become a liquid-solid system when the biodiesel reaches a certain content. In this work, we adopted a two-film theory and a steady state approximation assumption, then established a heterogeneous liquid-liquid-solid model in the first stage. After the diffusion coefficients on the liquid-liquid interface and the liquid-solid interface were calculated on the basis of the properties of the system, the theoretical value of biodiesel productivity changing with time was obtained. The predicted values were very near the experimental data, which indicated that the proposed models were suitable for the transesterification of soybean oil to biodiesel when solid bases were used as catalysts. Meanwhile, the model indicated that the transesterification reaction was controlled by both mass transfer and reaction. The total resistance will decrease with the increase in biodiesel yield in the liquid-liquid-solid stage. The solid base catalyst exhibited an activation energy range of 9-20 kcal/mol, which was consistent with the reported activation energy range of homogeneous catalysts.

The production of high efficiency Ziegler-Natta catalyst with dual active sites nature using cyclohexyl chloride as promoter with super activity and produced superior polyethylene with controllable molecular weight distribution.

PubMed

Seifali Abbas-Abadi, Mehrdad

2017-01-01

In the previous studies, the several halocarbons (HC) were tested as promoters for a Ti-based Ziegler-Natta (ZN) catalyst at different polymerization conditions. The Results showed that chloro cyclohexane has the best operation in catalyst activity, polymer particle size growth, hydrogen responsibility and wax reduction too. For the first time in this study, the effect of Al/Ti ratio on the optimum HC/Ti ratio has been considered and the results showed that the optimum HC/Ti ratio depends on the Al/Ti ratio directly. In the optimum HC/Ti ratio, the catalyst activity and hydrogen responsibility ratio of the catalyst increase up to 125 and 55% respectively. The acceptable growth of polymer powder up to 46%, lower flow rate ratio (FRR) up to 19% and decrease of wax amount up to 12%, completed the promotion results. Furthermore, in the next part of this study and as key note, a little dose of halocarbon was used in the catalyst preparation to produce the special catalysts with dual active sites. In the catalyst preparation, the concentration of each active sites depends on the halocarbon amount and it can control the molecular weight distribution of the produced polyethylene; because each active sites have different response to hydrogen. The halocarbon based catalysts showed the remarkable effect on the catalyst activity, the molecular weight and especially molecular weight distribution (MWD). The flow rate ratio and MWD could be increased up to 77 and 88% respectively as the main result of halocarbon addition during the catalyst preparation.

The production of high efficiency Ziegler–Natta catalyst with dual active sites nature using cyclohexyl chloride as promoter with super activity and produced superior polyethylene with controllable molecular weight distribution

PubMed Central

Seifali Abbas-Abadi, Mehrdad

2017-01-01

Abstract In the previous studies, the several halocarbons (HC) were tested as promoters for a Ti-based Ziegler–Natta (ZN) catalyst at different polymerization conditions. The Results showed that chloro cyclohexane has the best operation in catalyst activity, polymer particle size growth, hydrogen responsibility and wax reduction too. For the first time in this study, the effect of Al/Ti ratio on the optimum HC/Ti ratio has been considered and the results showed that the optimum HC/Ti ratio depends on the Al/Ti ratio directly. In the optimum HC/Ti ratio, the catalyst activity and hydrogen responsibility ratio of the catalyst increase up to 125 and 55% respectively. The acceptable growth of polymer powder up to 46%, lower flow rate ratio (FRR) up to 19% and decrease of wax amount up to 12%, completed the promotion results. Furthermore, in the next part of this study and as key note, a little dose of halocarbon was used in the catalyst preparation to produce the special catalysts with dual active sites. In the catalyst preparation, the concentration of each active sites depends on the halocarbon amount and it can control the molecular weight distribution of the produced polyethylene; because each active sites have different response to hydrogen. The halocarbon based catalysts showed the remarkable effect on the catalyst activity, the molecular weight and especially molecular weight distribution (MWD). The flow rate ratio and MWD could be increased up to 77 and 88% respectively as the main result of halocarbon addition during the catalyst preparation. PMID:29491824

Flavin redox bifurcation as a mechanism for controlling the direction of electron flow during extracellular electron transfer.

PubMed

Okamoto, Akihiro; Hashimoto, Kazuhito; Nealson, Kenneth H

2014-10-06

The iron-reducing bacterium Shewanella oneidensis MR-1 has a dual directional electronic conduit involving 40 heme redox centers in flavin-binding outer-membrane c-type cytochromes (OM c-Cyts). While the mechanism for electron export from the OM c-Cyts to an anode is well understood, how the redox centers in OM c-Cyts take electrons from a cathode has not been elucidated at the molecular level. Electrochemical analysis of live cells during switching from anodic to cathodic conditions showed that altering the direction of electron flow does not require gene expression or protein synthesis, but simply redox potential shift about 300 mV for a flavin cofactor interacting with the OM c-Cyts. That is, the redox bifurcation of the riboflavin cofactor in OM c-Cyts switches the direction of electron conduction in the biological conduit at the cell-electrode interface to drive bacterial metabolism as either anode or cathode catalysts. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dual membrane hollow fiber fuel cell and method of operating same

NASA Technical Reports Server (NTRS)

Ingham, J. D.; Lawson, D. D. (Inventor)

1978-01-01

A gaseous fuel cell is described which includes a pair of electrodes formed by open-ended, ion-exchange hollow fibers, each having a layer of metal catalyst deposited on the inner surface and large surface area current collectors such as braided metal mesh in contact with the metal catalyst layer. A fuel cell results when the electrodes are immersed in electrolytes and electrically connected. As hydrogen and oxygen flow through the bore of the fibers, oxidation and reduction reactions develop an electrical potential. Since the hollow fiber configuration provides large electrode area per unit volume and intimate contact between fuel and oxidizer at the interface, and due to the low internal resistance of the electrolyte, high power densities can be obtained.

Longitudinal Hierarchy Co3O4 Mesocrystals with High-dense Exposure Facets and Anisotropic Interfaces for Direct-Ethanol Fuel Cells.

PubMed

Hassen, Diab; El-Safty, Sherif A; Tsuchiya, Koichi; Chatterjee, Abhijit; Elmarakbi, Ahmed; Shenashen, Mohamed A; Sakai, Masaru

2016-04-14

Novel electrodes are needed for direct ethanol fuel cells with improved quality. Hierarchical engineering can produce catalysts composed of mesocrystals with many exposed active planes and multi-diffused voids. Here we report a simple, one-pot, hydrothermal method for fabricating Co3O4/carbon/substrate electrodes that provides control over the catalyst mesocrystal morphology (i.e., corn tubercle pellets or banana clusters oriented along nanotube domains, or layered lamina or multiple cantilevered sheets). These morphologies afforded catalysts with a high density of exposed active facets, a diverse range of mesopores in the cage interior, a window architecture, and vertical alignment to the substrate, which improved efficiency in an ethanol electrooxidation reaction compared with a conventional platinum/carbon electrode. On the atomic scale, the longitudinally aligned architecture of the Co3O4 mesocrystals resulted in exposed low- and high-index single and interface surfaces that had improved electron transport and diffusion compared with currently used electrodes.

Longitudinal Hierarchy Co3O4 Mesocrystals with High-dense Exposure Facets and Anisotropic Interfaces for Direct-Ethanol Fuel Cells

NASA Astrophysics Data System (ADS)

Hassen, Diab; El-Safty, Sherif A.; Tsuchiya, Koichi; Chatterjee, Abhijit; Elmarakbi, Ahmed; Shenashen, Mohamed. A.; Sakai, Masaru

2016-04-01

Novel electrodes are needed for direct ethanol fuel cells with improved quality. Hierarchical engineering can produce catalysts composed of mesocrystals with many exposed active planes and multi-diffused voids. Here we report a simple, one-pot, hydrothermal method for fabricating Co3O4/carbon/substrate electrodes that provides control over the catalyst mesocrystal morphology (i.e., corn tubercle pellets or banana clusters oriented along nanotube domains, or layered lamina or multiple cantilevered sheets). These morphologies afforded catalysts with a high density of exposed active facets, a diverse range of mesopores in the cage interior, a window architecture, and vertical alignment to the substrate, which improved efficiency in an ethanol electrooxidation reaction compared with a conventional platinum/carbon electrode. On the atomic scale, the longitudinally aligned architecture of the Co3O4 mesocrystals resulted in exposed low- and high-index single and interface surfaces that had improved electron transport and diffusion compared with currently used electrodes.

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

Kattel, Shyam; Liu, Ping; Chen, Jingguang G.

The chemical transformation of CO 2 not only mitigates the anthropogenic CO 2 emission into the Earth’s atmosphere but also produces carbon compounds that can be used as precursors for the production of chemicals and fuels. The activation and conversion of CO 2 can be achieved on multifunctional catalytic sites available at the metal/oxide interface by taking advantage of the synergy between the metal nanoparticles and oxide support. In this paper, we look at the recent progress in mechanistic studies of CO 2 hydrogenation to C1 (CO, CH 3OH, and CH 4) compounds on metal/oxide catalysts. On this basis, wemore » are able to provide a better understanding of the complex reaction network, grasp the capability of manipulating structure and combination of metal and oxide at the interface in tuning selectivity, and identify the key descriptors to control the activity and, in particular, the selectivity of catalysts. In conclusion, we also discuss challenges and future research opportunities for tuning the selective conversion of CO 2 on metal/oxide catalysts.« less

Longitudinal Hierarchy Co3O4 Mesocrystals with High-dense Exposure Facets and Anisotropic Interfaces for Direct-Ethanol Fuel Cells

PubMed Central

Hassen, Diab; El-Safty, Sherif A.; Tsuchiya, Koichi; Chatterjee, Abhijit; Elmarakbi, Ahmed; Shenashen, Mohamed. A.; Sakai, Masaru

2016-01-01

Novel electrodes are needed for direct ethanol fuel cells with improved quality. Hierarchical engineering can produce catalysts composed of mesocrystals with many exposed active planes and multi-diffused voids. Here we report a simple, one-pot, hydrothermal method for fabricating Co3O4/carbon/substrate electrodes that provides control over the catalyst mesocrystal morphology (i.e., corn tubercle pellets or banana clusters oriented along nanotube domains, or layered lamina or multiple cantilevered sheets). These morphologies afforded catalysts with a high density of exposed active facets, a diverse range of mesopores in the cage interior, a window architecture, and vertical alignment to the substrate, which improved efficiency in an ethanol electrooxidation reaction compared with a conventional platinum/carbon electrode. On the atomic scale, the longitudinally aligned architecture of the Co3O4 mesocrystals resulted in exposed low- and high-index single and interface surfaces that had improved electron transport and diffusion compared with currently used electrodes. PMID:27075551

Atomic force microscopy of atomic-scale ledges and etch pits formed during dissolution of quartz

NASA Technical Reports Server (NTRS)

Gratz, A. J.; Manne, S.; Hansma, P. K.

1991-01-01

The processes involved in the dissolution and growth of crystals are closely related. Atomic force microscopy (AFM) of faceted pits (called negative crystals) formed during quartz dissolution reveals subtle details of these underlying physical mechanisms for silicates. In imaging these surfaces, the AFM detected ledges less than 1 nm high that were spaced 10 to 90 nm apart. A dislocation pit, invisible to optical and scanning electron microscopy measurements and serving as a ledge source, was also imaged. These observations confirm the applicability of ledge-motion models to dissolution and growth of silicates; coupled with measurements of dissolution rate on facets, these methods provide a powerful tool for probing mineral surface kinetics.

Combinatorial electrochemical synthesis and screening of Pt-WO3 catalysts for electro-oxidation of methanol

NASA Astrophysics Data System (ADS)

Jayaraman, Shrisudersan; Baeck, Sung-Hyeon; Jaramillo, Thomas F.; Kleiman-Shwarsctein, Alan; McFarland, Eric W.

2005-06-01

An automated system for high-throughput electrochemical synthesis and screening of fuel cell electro-oxidation catalysts is described. This system consists of an electrode probe that contains counter and reference electrodes that can be positioned inside an array of electrochemical cells created within a polypropylene block. The electrode probe is attached to an automated of X-Y-Z motion system. An externally controlled potentiostat is used to apply the electrochemical potential to the catalyst substrate. The motion and electrochemical control are integrated using a user-friendly software interface. During automated synthesis the deposition potential and/or current may be controlled by a pulse program triggered by the software using a data acquisition board. The screening includes automated experiments to obtain cyclic voltammograms. As an example, a platinum-tungsten oxide (Pt-WO3) library was synthesized and characterized for reactivity towards methanol electro-oxidation.

43 CFR 3832.22 - How much land may I include in my mining claim?

Code of Federal Regulations, 2011 CFR

2011-10-01

... claims. Lode claims must not exceed 1,500 by 600 feet. If there is a vein, lode, or ledge, each lode claim is limited to a maximum of 1,500 feet along the course of the vein, lode, or ledge and a maximum of 300 feet in width on each side of the middle of the vein, lode, or ledge. (b) Placer claims. (1...

Microfluidic on-chip fluorescence-activated interface control system

PubMed Central

Haiwang, Li; Nguyen, N. T.; Wong, T. N.; Ng, S. L.

2010-01-01

A microfluidic dynamic fluorescence-activated interface control system was developed for lab-on-a-chip applications. The system consists of a straight rectangular microchannel, a fluorescence excitation source, a detection sensor, a signal conversion circuit, and a high-voltage feedback system. Aqueous NaCl as conducting fluid and aqueous glycerol as nonconducting fluid were introduced to flow side by side into the straight rectangular microchannel. Fluorescent dye was added to the aqueous NaCl to work as a signal representing the interface position. Automatic control of the liquid interface was achieved by controlling the electroosmotic effect that exists only in the conducting fluid using a high-voltage feedback system. A LABVIEW program was developed to control the output of high-voltage power supply according the actual interface position, and then the interface position is modified as the output of high-voltage power supply. At last, the interface can be moved to the desired position automatically using this feedback system. The results show that the system presented in this paper can control an arbitrary interface location in real time. The effects of viscosity ratio, flow rates, and polarity of electric field were discussed. This technique can be extended to switch the sample flow and droplets automatically. PMID:21173886

Fuel cell generator with fuel electrodes that control on-cell fuel reformation

DOEpatents

Ruka, Roswell J [Pittsburgh, PA; Basel, Richard A [Pittsburgh, PA; Zhang, Gong [Murrysville, PA

2011-10-25

A fuel cell for a fuel cell generator including a housing including a gas flow path for receiving a fuel from a fuel source and directing the fuel across the fuel cell. The fuel cell includes an elongate member including opposing first and second ends and defining an interior cathode portion and an exterior anode portion. The interior cathode portion includes an electrode in contact with an oxidant flow path. The exterior anode portion includes an electrode in contact with the fuel in the gas flow path. The anode portion includes a catalyst material for effecting fuel reformation along the fuel cell between the opposing ends. A fuel reformation control layer is applied over the catalyst material for reducing a rate of fuel reformation on the fuel cell. The control layer effects a variable reformation rate along the length of the fuel cell.

Controlled growth of vertically aligned carbon nanotubes on metal substrates

NASA Astrophysics Data System (ADS)

Gao, Zhaoli

Carbon nanotube (CNT) is a fascinating material with extraordinary electrical thermal and mechanical properties. Growing vertically aligned CNT (VACNT) arrays on metal substrates is an important step in bringing CNT into practical applications such as thermal interface materials (TIMs) and microelectrodes. However, the growth process is challenging due to the difficulties in preventing catalyst diffusion and controlling catalyst dewetting on metal substrates with physical surface heterogeneity. In this work, the catalyst diffusion mechanism and catalyst dewetting theory were studied for the controlled growth of VACNTs on metal substrates. The diffusion time of the catalyst, the diffusion coefficients for the catalyst in the substrate materials and the number density of catalyst nanoparticles after dewetting are identified as the key parameters, based on which three strategies are developed. Firstly, a fast-heating catalyst pretreatment strategy was used, aiming at preserving the amount of catalyst prior to CNT growth by reducing the catalyst diffusion time. The catalyst lifetime is extended from half an hour to one hour on a patterned Al thin film and a VACNT height of 106 mum, about twenty fold of that reported in the literature, was attained. Secondly, a diffusion barrier layer strategy is employed for a reduction of catalyst diffusion into the substrate materials. Enhancement of VACNT growth on Cu substrates was achieved by adopting a conformal Al2O 3 diffusion barrier layer fabricated by a specially designed atomic layer deposition (ALD) system. Lastly, a novel catalyst glancing angle deposition (GLAD) strategy is performed to manipulate the morphology of a relatively thick catalyst on metal substrates with physical surface heterogeneity, aiming to obtain uniform and dense catalyst nanoparticles after dewetting in the pretreatment process for enhanced VACNT growth. We are able to control the VACNT growth conditions on metal substrates in terms of their distribution, heights and alignments. Catalyst loss is controlled by the catalyst diffusion time and catalyst diffusion coefficients. A shorter catalyst diffusion time and smaller diffusion coefficient enhance VACNT growth on metals due to reduced catalyst loss during the pretreatment process. The dewetting behaviors of the thin film catalysts are influenced by the physical surface heterogeneity of the substrates which leads to non-uniform growth of VACNTs. The GLAD process facilitates the deposition of a relatively thick catalyst layer for the creation of dense and uniform catalyst nanoparticles. Applications of VACNT-metal structures in TIMs and microelectrodes are demonstrated. The VACNT-TIMs fabricated on Al alloy substrates have a typical thermal contact resistivity of 17.1 mm2˙K/W and their effective application in high-brightness LED thermal management was demonstrated. Electrochemical characterization was carried out on VACNT microelectrodes for the development of high resolution retinal prostheses and a satisfactory electrochemical property was again demonstrated.

Reaction pathways involved in CH4 conversion on Pd/Al2O3 catalysts : TAP as a powerful tool for the elucidation of the effective role of the metal/support interface

NASA Astrophysics Data System (ADS)

Granger, Pascal

2016-02-01

Temporal Analysis of Products (TAP) reactor offers an alternative to draw direct structure/activity relationships checked on Natural Gas-fuelled Vehicle (NGV) catalysts Determination of accurate kinetic constants for methane adsorption from single pulse experiments and subsequent investigation of sequential surface reactions from alternative CH4/O2 pulse experiments provides a straightforward visualization of the involvement of the metal/support interface on freshly-prepared catalysts and the loss of this effect on aged single palladium based catalysts.

MTBE Hydrolysis in Dilute Aqueous Solution Using Heterogeneous Strong Acid Catalysts

NASA Astrophysics Data System (ADS)

Rixey, W. G.

2003-12-01

The objective of this research has been the development of a potential in situ catalytic process for the hydrolysis of methyl tertiary butyl ether (MTBE) to tertiary butyl alcohol (TBA) and methanol in ground water. Bench-scale batch reactor studies were conducted over a temperature range of 23 deg C to 50 deg C with several heterogeneous strong acid catalysts to obtain rates of hydrolysis of MTBE to TBA and methanol at dilute concentrations in water. Continuous flow experiments were then conducted to obtain kinetic data over a temperature range of 15 deg C to 50 deg C for various flow rates for the most active catalysts. It was found that the batch and continuous flow experiments yielded similar intrinsic kinetic rate constants when sorption of MTBE to the catalyst was accounted for. Additional fixed-bed experiments were conducted with deionized water and 0.005 M CaCl2 feed solutions containing 100 mg/L MTBE, respectively, to assess the deactivation of the catalyst, and deactivation was found to be controlled by ion exchange of H+ in the catalyst with Ca+2 in the feed. Our results indicate that, for low to moderate groundwater velocities and cation concentrations at ambient temperatures, an in situ reactive barrier process using the most active catalysts studied in this research could be a viable process in terms of both suitable conversion of MTBE and catalyst life. Although application to in situ remediation is emphasized, the results of this research are also applicable to ex-situ groundwater treatment.

Direct deposit of catalyst on the membrane of direct feed fuel cells

NASA Technical Reports Server (NTRS)

Chun, William (Inventor); Narayanan, Sekharipuram R. (Inventor); Jeffries-Nakamura, Barbara (Inventor); Valdez, Thomas I. (Inventor); Linke, Juergen (Inventor)

2001-01-01

An improved direct liquid-feed fuel cell having a solid membrane electrolyte for electrochemical reactions of an organic fuel. Catalyst utilization and catalyst/membrane interface improvements are disclosed. Specifically, the catalyst layer is applied directly onto the membrane electrolyte.

Control of fluid flow during Bridgman crystal growth using low-frequency vibrational stirring

NASA Astrophysics Data System (ADS)

Zawilski, Kevin Thomas

The goal of this research program was to develop an in depth understanding of a promising new method for stirring crystal growth melts called coupled vibrational stirring (CVS). CVS is a mixing technique that can be used in sealed systems and produces rapid mixing through vortex flows. Under normal operating conditions, CVS uses low-frequency vibrations to move the growth crucible along a circular path, producing a surface wave and convection in the melt. This research focused on the application of CVS to the vertical Bridgman technique. CVS generated flows were directly studied using a physical modeling system containing water/glycerin solutions. Sodium nitrate was chosen as a model growth system because the growth process could be directly observed using a transparent furnace. Lead magnesium niobate-lead titanate (PMNT) was chosen as the third system because of its potential application for high performance solid state transducers and actuators. In this study, the critical parameters for controlling CVS flows in cylindrical Bridgman systems were established. One of the most important results obtained was the dependence of an axial velocity gradient on the vibrational frequency. By changing the frequency, the intensity of fluid flow at a given depth can be easily manipulated. The intensity of CVS flows near the crystal-melt interface was found to be important. When flow intensity near the interface increased during growth, large growth rate fluctuations and significant changes in interface shape were observed. To eliminate such fluctuations, a constant flow rate near the crystal-melt interface was maintained by decreasing the vibrational frequency. A continuous frequency ramp was found to be essential to grow crystals of good quality under strong CVS flows. CVS generated flows were also useful in controlling the shape of the growth interface. In the sodium nitrate system without stirring, high growth rates produced a very concave interface. By adjusting the flow intensity near the interface, CVS flows were able to flatten the growth interface under these extreme growth conditions.

Underwriters Laboratories Fire Tests of Sprayed Polyurethane Foam Applied Directly to Metal Roof Decks.

DTIC Science & Technology

1983-12-01

with 1 in. mineral wool insulation positioned on the tunnel ledges to provide a more positive seal. These tests will be identified with the letter "I...during test minus 4-1/2 ft igniting flame. (1) - Mineral wool insulation positioned on the tunnel ledges. -A41 File USNC77 Issued: 12-29-78... Mineral wool insulation positioned on the tunnel ledges. ,-A2 Fie SNśIsud: 12297 ;. "’"’._." "-...:. " ., , ’ "’" .k

Identification of D-region ledges of ionization by LF/VLF observations during a meteor shower

NASA Astrophysics Data System (ADS)

Rumi, G. C.

1982-09-01

It is shown that the perturbation produced by a meteor shower on a pair of LF and/or VLF standard frequency signals received after reflection on the lower ionosphere can be used for the detection of the nocturnal ledges which characterize the ionization profile of the D-region. The theoretical developments are applied to two specific sets of experimental data and the height and ionization of the ledges, together with other associated parameters, are determined.

Vibration measurements of automobile catalyst

NASA Astrophysics Data System (ADS)

Aatola, Seppo

1994-09-01

Vibration of catalyst cell, which is inside the casing of the catalyst, is difficult to measure with usual measuring instrumentation. When catalyst is in use, there is hot exhaust gas flow though the catalyst cell and temperature of the cell is approximately +900 degree(s)C. Therefore non-contact Laser- Doppler-Vibrometer was used to measure vibration velocity of the catalyst cell. The laser beam was directed towards the cell through pipe which was put through and welded to the casing of the catalyst. The outer end of the pipe was screw down with a tempered class to prevent exhaust gas flow from the pipe. The inner end of the pipe was open and few millimeters away from the measuring point. Catalyst was attached to the engine with two ways, rigidly close to the engine and flexible under the engine. The engine was running in test bench under controlled conditions. Vibration measurements were carried out during constant running speeds of the engine. Vibration signals were captured and analyzed with FFT-analyzer. Vibration of catalyst cell was strongest at running speed of 5000 rpm, from 10 to 20 g (1 g equals 9.81 ms-2), when catalyst was attached rigidly close to the engine. At running speed of 3000 rpm, vibration of catalyst cell was from 2 to 3 g in most cases, when catalyst was attached either rigidly or flexible to the engine. It is estimated that in real life, i.e. when catalyst is attached to car with same engine, vibration of catalyst cell at running speed of 5000 rpm is somewhere between 1 and 10 g. At running speed of 3000 rpm, which may be more often used when driving car (car speed approximately 100 kmh-1), vibration of catalyst cell is probably few g's.

Flow-Control Unit For Nitrogen And Hydrogen Gases

NASA Technical Reports Server (NTRS)

Chang, B. J.; Novak, D. W.

1990-01-01

Gas-flow-control unit installed and removed as one piece replaces system that included nine separately serviced components. Unit controls and monitors flows of nitrogen and hydrogen gases. Designed for connection via fluid-interface manifold plate, reducing number of mechanical fluid-interface connections from 18 to 1. Unit provides increasing reliability, safety, and ease of maintenance, and for reducing weight, volume, and power consumption.

Rahman Prize Lecture: Lattice Boltzmann simulation of complex states of flowing matter

NASA Astrophysics Data System (ADS)

Succi, Sauro

Over the last three decades, the Lattice Boltzmann (LB) method has gained a prominent role in the numerical simulation of complex flows across an impressively broad range of scales, from fully-developed turbulence in real-life geometries, to multiphase flows in micro-fluidic devices, all the way down to biopolymer translocation in nanopores and lately, even quark-gluon plasmas. After a brief introduction to the main ideas behind the LB method and its historical developments, we shall present a few selected applications to complex flow problems at various scales of motion. Finally, we shall discuss prospects for extreme-scale LB simulations of outstanding problems in the physics of fluids and its interfaces with material sciences and biology, such as the modelling of fluid turbulence, the optimal design of nanoporous gold catalysts and protein folding/aggregation in crowded environments.

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

Nano-scale observations of interface between lichen and basaltic rock: Pseudomorphic growth of amorphous silica on augite

NASA Astrophysics Data System (ADS)

Tamura, T.; Kyono, A.; Kebukawa, Y.; Takagi, S.

2017-12-01

Recently, lichens as the earliest colonizers of terrestrial habitats are recognized to accelerate the mineral degradation at the interface between lichens and surface rocks. Much interest has been therefore devoted in recent years to the weathering induced by the lichen colonization. Here, we report nano-scale observations of the interface between lichens and basaltic rock by TEM and STXM techniques. Some samples of basaltic rocks totally covered by lichens were collected from the 1986 lava flows on the northwest part of Izu-Oshima volcano, Japan. To prepare specimens for the nano-scale observation, we utilized the focused ion beam (FIB) system. The microstructure and local chemistry of the specimens were thoroughly investigated by TEM equipped with energy-dispersive X-ray spectroscopy (EDX). Chemical components and chemical heterogeneity at the interface were observed by scanning transmission X-ray microscopy (STXM) at Advanced Light Source branch line 5.3.2.2. The collected rocks were classified into the augite-pigeonite-bronzite basalt including 6 to 8% plagioclase phenocrysts. The lichens adhering to the rocks were mainly Stereocaulon vesuvianum, fruticose lichen, which are widespread over the study area. The metabolites of the Stereocaulon vesuvianum exhibited a mean pH of 4.5 and dominance by acids. The STEM-EDX observations revealed that the interface between augite and the lichen was completely covered with amorphous silica multilayer with a thickness of less than 1 µm. Ca L-edge XANES spectra of the augite showed that the energy profile of the absorption edge at 349 eV was varied with the depth from the surface, indicating that the M2 site coordination accommodating Ca2+ undergoes significant change in shape as a function of distance from the surface. This behavior results from the fact that the M2 site is more distorted and more flexible in the C2/c clinopyroxene phase. Taking into consideration that the S. vesuvianum can produce acidic organic compounds during metabolism, the amorphous silica multilayers observed at the interface were produced by mineral dissolution induced by the lichen, and formed as a pseudomorphic replacement of augite by amorphous silica.

Extending Tabletop XUV Spectroscopy to the Liquid Phase to Examine Transition Metal Catalysts

NASA Astrophysics Data System (ADS)

Benke, Kristin; Ryland, Elizabeth S.; Vura-Weis, Josh

2017-06-01

M-edge spectroscopy of first row transition metals (3p to 3d excitation) is the low energy analogue of more well-known K- and L-edge spectroscopy, but can be implemented without the use of a synchrotron. Instead, M-edge spectroscopy can be performed as a tabletop method, relying on high harmonic generation (HHG) to produce ultrashort (˜ 20 fs) pulses of extreme ultraviolet (XUV) light in the range of 10-100s of eV. We have shown tabletop M-edge spectroscopy to be a valuable tool in determining the electronic structure of metal-centered coordination complexes and have demonstrated its capacity to yield element-specific information about a compound's oxidation state, spin state, and ligand field. The power of this technique to distinguish these features makes it a promising addition to the arsenal of methods used to study metal-centered catalysts. A catalytic reaction can be initiated photochemically and the XUV probe can be used to track oxidative and structural changes to identify the key intermediates. Until recently tabletop XUV spectroscopy has been performed on thin film samples, but in order to examine homogeneous catalysis, the technique must be adapted to look at samples in the liquid phase. The challenges of adapting tabletop XUV spectroscopy to the liquid phase lie in the lower attenuation length of XUV light compared to soft and hard x-rays and the lower flux compared to synchrotron methods. As a result, the sample must be limited to a sub-micron thickness as well as isolated from the vacuum environment required for x-ray spectroscopy. I am developing a liquid flow cell that relies on confining the sample between two x-ray transmissive SiN membranes, as has been demonstrated for use at synchrotrons, but adapted to the unique difficulties encountered in tabletop XUV spectroscopy.

The surface plasmon-induced hot carrier effect on the catalytic activity of CO oxidation on a Cu2O/hexoctahedral Au inverse catalyst.

PubMed

Lee, Si Woo; Hong, Jong Wook; Lee, Hyunhwa; Wi, Dae Han; Kim, Sun Mi; Han, Sang Woo; Park, Jeong Young

2018-06-14

The intrinsic correlation between an enhancement of catalytic activity and the flow of hot electrons generated at metal-oxide interfaces suggests an intriguing way to control catalytic reactions and is a significant subject in heterogeneous catalysis. Here, we show surface plasmon-induced catalytic enhancement by the peculiar nanocatalyst design of hexoctahedral (HOH) Au nanocrystals (NCs) with Cu2O clusters. We found that this inverse catalyst comprising a reactive oxide for the catalytic portion and a metal as the source of electrons by localized surface plasmon resonance (localized SPR) exhibits a change in catalytic activity by direct hot electron transfer or plasmon-induced resonance energy transfer (PIRET) when exposed to light. We prepared two types of inverse catalysts, Cu2O at the vertex sites of HOH Au NCs (Cu2O/Au vertex site) and a HOH Au NC-Cu2O core-shell structure (HOH Au@Cu2O), to test the structural effect on surface plasmons. Under broadband light illumination, the Cu2O/Au vertex site catalyst showed 30-90% higher catalytic activity and the HOH Au@Cu2O catalyst showed 10-30% higher catalytic activity than when in the dark. Embedding thin SiO2 layers between the HOH Au NCs and the Cu2O verified that the dominant mechanism for the catalytic enhancement is direct hot electron transfer from the HOH Au to the Cu2O. Finite-difference time domain calculations show that a much stronger electric field was formed on the vertex sites after growing the Cu2O on the HOH Au NCs. These results imply that the catalytic activity is enhanced when hot electrons, created from photon absorption on the HOH Au metal and amplified by the presence of surface plasmons, are transferred to the reactive Cu2O.

Charge Transfer and Support Effects in Heterogeneous Catalysis

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

Hervier, Antoine

The kinetic, electronic and spectroscopic properties of two-dimensional oxide-supported catalysts were investigated in order to understand the role of charge transfer in catalysis. Pt/TiO 2 nanodiodes were fabricated and used as catalysts for hydrogen oxidation. During the reaction, the current through the diode, as well as its I-V curve, were monitored, while gas chromatography was used to measure the reaction rate. The current and the turnover rate were found to have the same temperature dependence, indicating that hydrogen oxidation leads to the non-adiabatic excitation of electrons in Pt. A fraction of these electrons have enough energy to ballistically transport throughmore » Pt and overcome the Schottky barrier at the interface with TiO 2. The yield for this phenomenon is on the order of 10 -4 electrons per product molecule formed, similar to what has been observed for CO oxidation and for the adsorption of many different molecules. The same Pt/TiO 2 system was used to compare currents in hydrogen oxidation and deuterium oxidation. The current through the diode under deuterium oxidation was found to be greater than under hydrogen oxidation by a factor of three. Weighted by the difference in turnover frequencies for the two isotopes, this would imply a chemicurrent yield 5 times greater for D 2 compared to H 2, contrary to what is expected given the higher mass of D 2. Reversible changes in the rectification factor of the diode are observed when switching between D 2 and H 2. These changes are a likely cause for the differences in current between the two isotopes. In the nanodiode experiments, surface chemistry leads to charge flow, suggesting the possibility of creating charge flow to tune surface chemistry. This was done first by exposing a Pt/Si diode to visible light while using it as a catalyst for H 2 oxidation. Absorption of the light in the Si, combined with the band bending at the interface, gives rise to a steady-state flow of hot holes to the surface. This leads to a decrease in turnover on the surface, an effect which is enhanced when a reverse bias is applied to the diode. Similar experiments were carried out for CO oxidation. On Pt/Si diodes, the reaction rate was found to increase when a forward bias was applied. When the diode was exposed to visible light and a reverse bias was applied, the rate was instead decreased. This implies that a flow of negative charges to the surface increases turnover, while positive charges decrease it. Charge flow in an oxide supported metal catalyst can be modified even without designing the catalyst as a solid state electronic device. This was done by doping stoichiometric and nonstoichiometric TiO 2 films with F, and using the resulting oxides as supports for Pt films. In the case of stoichiometric TiO 2, F was found to act as an n-type dopant, creating a population of filled electronic states just below the conduction band, and dramatically increasing the conductivity of the oxide film. The electrons in those states can transfer to surface O, activating it for reaction with CO, and leading to increased turnover for CO oxidation. This reinforces the hypothesis that CO oxidation is activated by a flow of negative charges to the surface. The same set of catalysts was used for methanol oxidation. The electronic properties of the TiO 2 films again correlated with the turnover rates, but also with selectivity. With stoichiometric TiO 2 as the support, F-doping caused an increase in selectivity toward the formation of partial oxidation products, formaldehyde and methyl formate, versus the total oxidation product, CO 2. With non-stoichiometric TiO 2, F-doping had the reverse effect. Ambient Pressure X-Ray Photoelectron Spectroscopy was used to investigate this F-doping effect in reaction conditions. In O 2 alone, and in CO oxidation conditions, the O1s spectrum showed a high binding energy peak that correlated in intensity with the activity of the different films: for stoichiometric films, the peak decreased in intensity with F-doping, while for nonstoichiometric films, the opposite was observed. No such changes were visible in the C1s spectrum, confirming the role of O activation in the reaction. This thesis adds to the body of knowledge on the importance of charge transfer at the metal-oxide interface in shaping the reactivity of heterogeneous catalysts, and provides examples of how this can be the basis for new methods to tune reactivity.« less

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

PubMed Central

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

2017-01-01

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

Simultaneous probing of bulk liquid phase and catalytic gas-liquid-solid interface under working conditions using attenuated total reflection infrared spectroscopy

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

Meemken, Fabian; Müller, Philipp; Hungerbühler, Konrad

Design and performance of a reactor set-up for attenuated total reflection infrared (ATR-IR) spectroscopy suitable for simultaneous reaction monitoring of bulk liquid and catalytic solid-liquid-gas interfaces under working conditions are presented. As advancement of in situ spectroscopy an operando methodology for gas-liquid-solid reaction monitoring was developed that simultaneously combines catalytic activity and molecular level detection at the catalytically active site of the same sample. Semi-batch reactor conditions are achieved with the analytical set-up by implementing the ATR-IR flow-through cell in a recycle reactor system and integrating a specifically designed gas feeding system coupled with a bubble trap. By the usemore » of only one spectrometer the design of the new ATR-IR reactor cell allows for simultaneous detection of the bulk liquid and the catalytic interface during the working reaction. Holding two internal reflection elements (IRE) the sample compartments of the horizontally movable cell are consecutively flushed with reaction solution and pneumatically actuated, rapid switching of the cell (<1 s) enables to quasi simultaneously follow the heterogeneously catalysed reaction at the catalytic interface on a catalyst-coated IRE and in the bulk liquid on a blank IRE. For a complex heterogeneous reaction, the asymmetric hydrogenation of 2,2,2-trifluoroacetophenone on chirally modified Pt catalyst the elucidation of catalytic activity/enantioselectivity coupled with simultaneous monitoring of the catalytic solid-liquid-gas interface is shown. Both catalytic activity and enantioselectivity are strongly dependent on the experimental conditions. The opportunity to gain improved understanding by coupling measurements of catalytic performance and spectroscopic detection is presented. In addition, the applicability of modulation excitation spectroscopy and phase-sensitive detection are demonstrated.« less

Fine structural features of nanoscale zero-valent iron characterized by spherical aberration corrected scanning transmission electron microscopy (Cs-STEM).

PubMed

Liu, Airong; Zhang, Wei-xian

2014-09-21

An angstrom-resolution physical model of nanoscale zero-valent iron (nZVI) is generated with a combination of spherical aberration corrected scanning transmission electron microscopy (Cs-STEM), selected area electron diffraction (SAED), energy-dispersive X-ray spectroscopy (EDS) and electron energy-loss spectroscopy (EELS) on the Fe L-edge. Bright-field (BF), high-angle annular dark-field (HAADF) and secondary electron (SE) imaging of nZVI acquired by a Hitachi HD-2700 STEM show near atomic resolution images and detailed morphological and structural information of nZVI. The STEM-EDS technique confirms that the fresh nZVI comprises of a metallic iron core encapsulated with a thin layer of iron oxides or oxyhydroxides. SAED patterns of the Fe core suggest the polycrystalline structure in the metallic core and amorphous nature of the oxide layer. Furthermore, Fe L-edge of EELS shows varied structural features from the innermost Fe core to the outer oxide shell. A qualitative analysis of the Fe L(2,3) edge fine structures reveals that the shell of nZVI consists of a mixed Fe(II)/Fe(III) phase close to the Fe (0) interface and a predominantly Fe(III) at the outer surface of nZVI.

The potential of model studies for the understanding of catalyst poisoning and temperature effects in polymer electrolyte fuel cell reactions

NASA Astrophysics Data System (ADS)

Behm, R. J.; Jusys, Z.

In this contribution we demonstrate the potential of model studies for the understanding of electrocatalytic reactions in low-temperature polymer electrolyte fuel cells (PEFCs) operated by H 2-rich anode feed gas, in particular of the role of temperature effects and catalyst poisoning. Reviewing previous work from our laboratory and, for better comparison, focussing on carbon-supported Pt catalysts, the important role of using fuel cell relevant reaction and mass transport conditions will be outlined. The latter conditions include continuous reaction, elevated temperatures, realistic supported catalyst materials and controlled mass transport. The data show the importance of combining electrochemical techniques such as rotating disc electrode (RDE), wall-jet and flow cell measurements, and on-line differential electrochemical mass spectrometry (DEMS) under controlled mass transport conditions.

Minisparker profiles from Jeffreys Ledge and adjacent areas in the western Gulf of Maine

USGS Publications Warehouse

Eskenasy, Diane M.; Bailey, Norman G.

1980-01-01

A total of 250 kilometers of single-channel seismic-reflection data (28 minisparker profiles) were collected in the coastal waters of Massachusetts, north of and immediately south of Cape Ann, and on the western flank of Jeffreys Ledge, western Gulf of Maine, during the September 1978 cruise of the R/V ASTERIAS. The survey was conducted by the U.S. Geological Survey as part of the Massachusetts Cooperative Marine Geologic Program.The seismic systems used included a 1Del Norte minisparker and streamer, an Energy International Streamer, and EPC 3200 and 4100 recorders. Navigational control was established by Radar and Loran-C. The Loran-C navigation data were recorded on a Northstar 6000 system.The purpose of the cruise was to discover the significance and extent of the folded and faulted internal reflections that were first noticed on the esternmost tip of Jeffreys Ledge in line 14 of esternmost tip of Jeffreys Ledge in line 14 of rninisparker data from the 1976 R/V FAY 023 cruise.Sixteen northwest-trending lines were run off Cape Ann to investigate the deformed reflectors, now thought to represent a moraine formed by readvance of continental ice over the last glacial marine Presurnpscot Formation. Lines north and south of Cape Ann were run to locate the offshore extension of the Clinton-Newbury and Bloody Bluff fault systems.The original records can be studied at the U.S. Geological Survey offices at Woods Hole, Mass. Microfilm copies of the records can be purchased only from the National Geophysical and Solar-Terrestrial Data Center, NOAA/EDIS/NGSDC, Code D621, 325 Broadway; Boulder, CO 80303 (303-497-6338)

ρ-VOF: An interface sharpening method for gas-liquid flow simulation

NASA Astrophysics Data System (ADS)

Wang, Jiantao; Liu, Gang; Jiang, Xiong; Mou, Bin

2018-05-01

The study on simulation of compressible gas-liquid flow remains open. Popular methods are either confined to incompressible flow regime, or inevitably induce smear of the free interface. A new finite volume method for compressible two-phase flow simulation is contributed for this subject. First, the “heterogeneous equilibrium” assumption is introduced to the control volume, by hiring free interface reconstruction technology, the distribution of each component in the control volume is achieved. Next, AUSM+-up (advection upstream splitting method) scheme is employed to calculate the convective fluxes and pressure fluxes, with the contact discontinuity characteristic considered, followed by the update of the whole flow field. The new method features on density-based pattern and interface reconstruction technology from VOF (volume of fluid), thus we name it “ρ-VOF method”. Inherited from AUSM families and VOF, ρ-VOF behaves as an all-speed method, capable of simulating shock in gas-liquid flow, and preserving the sharpness of the free interface. Gas-liquid shock tube is simulated to evaluate the method, from which good agreement is obtained between the predicted results and those of the cited literature, meanwhile, sharper free interface is identified. Finally, the capability and validity of ρ-VOF method can be concluded in compressible gas-liquid flow simulation.

Rapid Inversion: Running Animals and Robots Swing like a Pendulum under Ledges

PubMed Central

Mongeau, Jean-Michel; McRae, Brian; Jusufi, Ardian; Birkmeyer, Paul; Hoover, Aaron M.; Fearing, Ronald; Full, Robert J.

2012-01-01

Escaping from predators often demands that animals rapidly negotiate complex environments. The smallest animals attain relatively fast speeds with high frequency leg cycling, wing flapping or body undulations, but absolute speeds are slow compared to larger animals. Instead, small animals benefit from the advantages of enhanced maneuverability in part due to scaling. Here, we report a novel behavior in small, legged runners that may facilitate their escape by disappearance from predators. We video recorded cockroaches and geckos rapidly running up an incline toward a ledge, digitized their motion and created a simple model to generalize the behavior. Both species ran rapidly at 12–15 body lengths-per-second toward the ledge without braking, dove off the ledge, attached their feet by claws like a grappling hook, and used a pendulum-like motion that can exceed one meter-per-second to swing around to an inverted position under the ledge, out of sight. We discovered geckos in Southeast Asia can execute this escape behavior in the field. Quantification of these acrobatic behaviors provides biological inspiration toward the design of small, highly mobile search-and-rescue robots that can assist us during natural and human-made disasters. We report the first steps toward this new capability in a small, hexapedal robot. PMID:22701594

Small-volume, ultrahigh-vacuum-compatible high-pressure reaction cell for combined kinetic and in situ IR spectroscopic measurements on planar model catalysts

NASA Astrophysics Data System (ADS)

Zhao, Z.; Diemant, T.; Häring, T.; Rauscher, H.; Behm, R. J.

2005-12-01

We describe the design and performance of a high-pressure reaction cell for simultaneous kinetic and in situ infrared reflection (IR) spectroscopic measurements on model catalysts at elevated pressures, between 10-3 and 103mbars, which can be operated both as batch reactor and as flow reactor with defined gas flow. The cell is attached to an ultrahigh-vacuum (UHV) system, which is used for sample preparation and also contains facilities for sample characterization. Specific for this design is the combination of a small cell volume, which allows kinetic measurements with high sensitivity under batch or continuous flow conditions, the complete isolation of the cell from the UHV part during UHV measurements, continuous temperature control during both UHV and high-pressure operation, and rapid transfer between UHV and high-pressure stage. Gas dosing is performed by a designed gas-handling system, which allows operation as flow reactor with calibrated gas flows at adjustable pressures. To study the kinetics of reactions on the model catalysts, a quadrupole mass spectrometer is connected to the high-pressure cell. IR measurements are possible in situ by polarization-modulation infrared reflection-absorption spectroscopy, which also allows measurements at elevated pressures. The performance of the setup is demonstrated by test measurements on the kinetics for CO oxidation and the CO adsorption on a Au /TiO2/Ru(0001) model catalyst film at 1-50 mbar total pressure.

Detailed Aggregate Resources Study, Dry Lake Valley, Nevada.

DTIC Science & Technology

1981-05-29

LOCAL SAND SOURCES IGENERALLY CYLINDERS. DRYING SHRINKAGE I COLLECTED WITHIN A FEW MILES OF CORRESPONDING LEDGE-ROCK SOURCES) SUPPLIED FINE MENS...COMPRESSIVE AND TENSILE STh LEDGE-ROCK SOURCES SUPPLIED COARSE AGGREGATES; LOCAL SAND SOURCES IGENERALLY CYLINDERS. DRYING SHRINKAGE COLLECTED WITHIN A FEW

Method and apparatus for controlling accidental releases of tritium

DOEpatents

Galloway, T.R.

1980-04-01

An improvement is described in a tritium control system based on a catalytic oxidation reactor wherein accidental releases of tritium into room air are controlled by flooding the catalytic oxidation reactor with hydrogen when the tritium concentration in the room air exceeds a specified limit. The sudden flooding with hydrogen heats the catalyst to a high temperature within seconds, thereby greatly increasing the catalytic oxidation rate of tritium to tritiated water vapor. Thus, the catalyst is heated only when needed. In addition to the heating effect, the hydrogen flow also swamps the tritium and further reduces the tritium release. 1 fig.

Method and apparatus for controlling accidental releases of tritium

DOEpatents

Galloway, Terry R. [Berkeley, CA

1980-04-01

An improvement in a tritium control system based on a catalytic oxidation reactor wherein accidental releases of tritium into room air are controlled by flooding the catalytic oxidation reactor with hydrogen when the tritium concentration in the room air exceeds a specified limit. The sudden flooding with hydrogen heats the catalyst to a high temperature within seconds, thereby greatly increasing the catalytic oxidation rate of tritium to tritiated water vapor. Thus, the catalyst is heated only when needed. In addition to the heating effect, the hydrogen flow also swamps the tritium and further reduces the tritium release.

Controlling band alignments by artificial interface dipoles at perovskite heterointerfaces

DOE PAGES

Yajima, Takeaki; Hikita, Yasuyuki; Minohara, Makoto; ...

2015-04-07

The concept ‘the interface is the device' is embodied in a wide variety of interfacial electronic phenomena and associated applications in oxide materials, ranging from catalysts and clean energy systems to emerging multifunctional devices. Many device properties are defined by the band alignment, which is often influenced by interface dipoles. On the other hand, the ability to purposefully create and control interface dipoles is a relatively unexplored degree of freedom for perovskite oxides, which should be particularly effective for such ionic materials. Here we demonstrate tuning the band alignment in perovskite metal-semiconductor heterojunctions over a broad range of 1.7 eV.more » This is achieved by the insertion of positive or negative charges at the interface, and the resultant dipole formed by the induced screening charge. This approach can be broadly used in applications where decoupling the band alignment from the constituent work functions and electron affinities can enhance device functionality.« less

Magnetism and electronic structure at the interface of a metal CaRuO3 and Mott insulator CaMnO3.

NASA Astrophysics Data System (ADS)

Boris, Alexander; Freeland, John; Kavich, Jerald; Lee, Ho Nyung; Yordanov, Petar; Khaliullin, Giniyat; Keimer, Bernhard; Chakhalian, Jak

2007-03-01

Recent advances in fabrication of ultra-thin complex oxide heterostructures have opened new opportunities to investigate possible novel quantum states at the correlated interfaces. With this aim we fabricated ultra-thin superlattices of CaMnO3(CMO)/CaRuO3(CRO) with the thickness of CRO layers from 1 to 12 unit cells by laser MBE. Electronic properties of CRO/CMO were investigated by soft x-ray spectroscopies at the L-edges of Mn and Ru. SQUID and optical reflectivity revealed a ferromagnetic thickness-independent transition at Tc 100K and CRO thickness-dependent negative magnetoresistance. This behavior is in marked contrast to the individual layers. At the interface we found a clear sign of net magnetic moment on Mn, which saturates only at magnetic field of 5T. Unlike CMO, similar measurements at the Ru L3-edge showed no detectable magnetism in the field up to 5T. Comparison with Ru references confirmed Ru(IV) oxidation state. These findings are in the sharp contrast with previously suggested models involving Ru(IV-V) valency exchange and thus reveal intricate nature of the interface between a metal and Mott insulator.

Dispersed catalysts for co-processing and coal liquefaction

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

Bockrath, B.; Parfitt, D.; Miller, R.

1995-12-31

The basic goal is to improve dispersed catalysts employed in the production of clean fuels from low value hydrocarbons. The immediate objective is to determine how the properties of the catalysts may be altered to match the demands placed on them by the properties of the feedstock, the qualities of the desired end products, and the economic constraints put upon the process. Several interrelated areas of the application of dispersed catalysts to co-processing and coal conversion are under investigation. The first involves control of the selectivity of MoS{sub 2} catalysts for HDN, HDS, and hydrogenation of aromatics. A second areamore » of research is the development and use of methods to evaluate dispersed catalysts by means of activity and selectivity tests. A micro-flow reactor has been developed for determining intrinsic reactivities using model compounds, and will be used to compare catalysts prepared in different ways. Micro-autoclaves will also be used to develop data in batch experiments at higher partial pressures of hydrogen. The third area under investigation concerns hydrogen spillover reactions between MoS{sub 2} catalysts and carbonaceous supports. Preliminary results obtained by monitoring H{sub 2}/D{sub 2} exchange reactions with a pulse-flow microreactor indicate the presence of spillover between MoS{sub 2} and a graphitic carbon. A more complete study will be made at a later stage of the project. Accomplishments and conclusions are discussed.« less

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

PubMed

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

2018-03-14

Defying text definitions of wet etching, metal-assisted chemical etching (MacEtch), a solution-based, damage-free semiconductor etching method, is directional, where the metal catalyst film sinks with the semiconductor etching front, producing 3D semiconductor structures that are complementary to the metal catalyst film pattern. The same recipe that works perfectly to produce ordered array of nanostructures for single-crystalline Si (c-Si) fails completely when applied to polycrystalline Si (poly-Si) with the same doping type and level. Another long-standing challenge for MacEtch is the difficulty of uniformly etching across feature sizes larger than a few micrometers because of the nature of lateral etching. The issue of interface control between the catalyst and the semiconductor in both lateral and vertical directions over time and over distance needs to be systematically addressed. Here, we present a self-anchored catalyst (SAC) MacEtch method, where a nanoporous catalyst film is used to produce nanowires through the pinholes, which in turn physically anchor the catalyst film from detouring as it descends. The systematic vertical etch rate study as a function of porous catalyst diameter from 200 to 900 nm shows that the SAC-MacEtch not only confines the etching direction but also enhances the etch rate due to the increased liquid access path, significantly delaying the onset of the mass-transport-limited critical diameter compared to nonporous catalyst c-Si counterpart. With this enhanced mass transport approach, vias on multistacks of poly-Si/SiO 2 are also formed with excellent vertical registry through the polystack, even though they are separated by SiO 2 which is readily removed by HF alone with no anisotropy. In addition, 320 μm square through-Si-via (TSV) arrays in 550 μm thick c-Si are realized. The ability of SAC-MacEtch to etch through poly/oxide/poly stack as well as more than half millimeter thick silicon with excellent site specificity for a wide range of feature sizes has significant implications for 2.5D/3D photonic and electronic device applications.

A transmission infrared cell design for temperature-controlled adsorption and reactivity studies on heterogeneous catalysts

NASA Astrophysics Data System (ADS)

Cybulskis, Viktor J.; Harris, James W.; Zvinevich, Yury; Ribeiro, Fabio H.; Gounder, Rajamani

2016-10-01

A design is presented for a versatile transmission infrared cell that can interface with an external vacuum manifold to undergo in situ gas treatments and receive controlled doses of various adsorbates and probe molecules, allowing characterization of heterogeneous catalyst surfaces in order to identify and quantify active sites and adsorbed surface species. Critical design characteristics include customized temperature control for operation between cryogenic and elevated temperatures (100-1000 K) and modified Cajon fittings for operation over a wide pressure range (10-2-103 Torr) that eliminates the complications introduced when using sealants or flanges to secure cell windows. The customized, hand-tightened Cajon fittings simplify operation of the cell compared to previously reported designs, because they allow for rapid cell assembly and disassembly and, in turn, replacement of catalyst samples. In order to validate the performance of the cell, transmission infrared spectroscopic experiments are reported to characterize the Brønsted and Lewis acid sites present in H-beta and H-mordenite zeolites using cryogenic adsorption of CO (<150 K).

A transmission infrared cell design for temperature-controlled adsorption and reactivity studies on heterogeneous catalysts.

PubMed

Cybulskis, Viktor J; Harris, James W; Zvinevich, Yury; Ribeiro, Fabio H; Gounder, Rajamani

2016-10-01

A design is presented for a versatile transmission infrared cell that can interface with an external vacuum manifold to undergo in situ gas treatments and receive controlled doses of various adsorbates and probe molecules, allowing characterization of heterogeneous catalyst surfaces in order to identify and quantify active sites and adsorbed surface species. Critical design characteristics include customized temperature control for operation between cryogenic and elevated temperatures (100-1000 K) and modified Cajon fittings for operation over a wide pressure range (10 -2 -10 3 Torr) that eliminates the complications introduced when using sealants or flanges to secure cell windows. The customized, hand-tightened Cajon fittings simplify operation of the cell compared to previously reported designs, because they allow for rapid cell assembly and disassembly and, in turn, replacement of catalyst samples. In order to validate the performance of the cell, transmission infrared spectroscopic experiments are reported to characterize the Brønsted and Lewis acid sites present in H-beta and H-mordenite zeolites using cryogenic adsorption of CO (<150 K).

Ultrathin Coating of Confined Pt Nanocatalysts by Atomic Layer Deposition for Enhanced Catalytic Performance in Hydrogenation Reactions.

PubMed

Wang, Meihua; Gao, Zhe; Zhang, Bin; Yang, Huimin; Qiao, Yan; Chen, Shuai; Ge, Huibin; Zhang, Jiankang; Qin, Yong

2016-06-13

Metal-support interfaces play a prominent role in heterogeneous catalysis. However, tailoring the metal-support interfaces to realize full utilization remains a major challenge. In this work, we propose a graceful strategy to maximize the metal-oxide interfaces by coating confined nanoparticles with an ultrathin oxide layer. This is achieved by sequential deposition of ultrathin Al2 O3 coats, Pt, and a thick Al2 O3 layer on carbon nanocoils templates by atomic layer deposition (ALD), followed by removal of the templates. Compared with the Pt catalysts confined in Al2 O3 nanotubes without the ultrathin coats, the ultrathin coated samples have larger Pt-Al2 O3 interfaces. The maximized interfaces significantly improve the activity and the protecting Al2 O3 nanotubes retain the stability for hydrogenation reactions of 4-nitrophenol. We believe that applying ALD ultrathin coats on confined catalysts is a promising way to achieve enhanced performance for other catalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Interactions Between Ocean Circulation and Topography in Icy Worlds

NASA Astrophysics Data System (ADS)

Goodman, J. C.

2018-05-01

To what extent does topography at the water-rock interface control the general circulation patterns of icy world oceans? And contrariwise, to what extent does liquid flow control the topography at the ice-water interface (or interfaces)?

Turbine assembly containing an inner shroud

DOEpatents

Bagepalli, Bharat Sampathkumaran; Corman, Gregory Scot; Dean, Anthony John; DiMascio, Paul Stephen; Mirdamadi, Massoud

2000-01-01

A turbine assembly having a turbine stator, a ceramic inner shroud, and a first spring. The stator has a longitudinal axis and an outer shroud block with opposing and longitudinally outward facing first and second sides. The first side has a longitudinally outward projecting first ledge and has a first side portion located radially outward of the first ledge. The ceramic inner shroud has a first hook portion longitudinally and radially surrounding the first ledge. The first spring is attached to one of the first side portion and the first hook portion and unattachedly and resiliently contacts the other of the first side portion and the first hook portion.

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

PubMed

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

2008-09-01

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

Structure and application of an interface program between a geographic-information system and a ground-water flow model

USGS Publications Warehouse

Van Metre, P.C.

1990-01-01

A computer-program interface between a geographic-information system and a groundwater flow model links two unrelated software systems for use in developing the flow models. The interface program allows the modeler to compile and manage geographic components of a groundwater model within the geographic information system. A significant savings of time and effort is realized in developing, calibrating, and displaying the groundwater flow model. Four major guidelines were followed in developing the interface program: (1) no changes to the groundwater flow model code were to be made; (2) a data structure was to be designed within the geographic information system that follows the same basic data structure as the groundwater flow model; (3) the interface program was to be flexible enough to support all basic data options available within the model; and (4) the interface program was to be as efficient as possible in terms of computer time used and online-storage space needed. Because some programs in the interface are written in control-program language, the interface will run only on a computer with the PRIMOS operating system. (USGS)

Multistep continuous-flow synthesis of (R)- and (S)-rolipram using heterogeneous catalysts

NASA Astrophysics Data System (ADS)

Tsubogo, Tetsu; Oyamada, Hidekazu; Kobayashi, Shū

2015-04-01

Chemical manufacturing is conducted using either batch systems or continuous-flow systems. Flow systems have several advantages over batch systems, particularly in terms of productivity, heat and mixing efficiency, safety, and reproducibility. However, for over half a century, pharmaceutical manufacturing has used batch systems because the synthesis of complex molecules such as drugs has been difficult to achieve with continuous-flow systems. Here we describe the continuous-flow synthesis of drugs using only columns packed with heterogeneous catalysts. Commercially available starting materials were successively passed through four columns containing achiral and chiral heterogeneous catalysts to produce (R)-rolipram, an anti-inflammatory drug and one of the family of γ-aminobutyric acid (GABA) derivatives. In addition, simply by replacing a column packed with a chiral heterogeneous catalyst with another column packed with the opposing enantiomer, we obtained antipole (S)-rolipram. Similarly, we also synthesized (R)-phenibut, another drug belonging to the GABA family. These flow systems are simple and stable with no leaching of metal catalysts. Our results demonstrate that multistep (eight steps in this case) chemical transformations for drug synthesis can proceed smoothly under flow conditions using only heterogeneous catalysts, without the isolation of any intermediates and without the separation of any catalysts, co-products, by-products, and excess reagents. We anticipate that such syntheses will be useful in pharmaceutical manufacturing.

Tethered catalysts for the hydration of carbon dioxide

DOEpatents

Valdez, Carlos A; Satcher, Jr., Joe H; Aines, Roger D; Wong, Sergio E; Baker, Sarah E; Lightstone, Felice C; Stolaroff, Joshuah K

2014-11-04

A system is provided that substantially increases the efficiency of CO.sub.2 capture and removal by positioning a catalyst within an optimal distance from the air-liquid interface. The catalyst is positioned within the layer determined to be the highest concentration of carbon dioxide. A hydrophobic tether is attached to the catalyst and the hydrophobic tether modulates the position of the catalyst within the liquid layer containing the highest concentration of carbon dioxide.

Hydrogen recombiner catalyst test supporting data

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

Britton, M.D.

1995-01-19

This is a data package supporting the Hydrogen Recombiner Catalyst Performance and Carbon Monoxide Sorption Capacity Test Report, WHC-SD-WM-TRP-211, Rev 0. This report contains 10 appendices which consist of the following: Mass spectrometer analysis reports: HRC samples 93-001 through 93-157; Gas spectrometry analysis reports: HRC samples 93-141 through 93-658; Mass spectrometer procedure PNL-MA-299 ALO-284; Alternate analytical method for ammonia and water vapor; Sample log sheets; Job Safety analysis; Certificate of mixture analysis for feed gases; Flow controller calibration check; Westinghouse Standards Laboratory report on Bois flow calibrator; and Sorption capacity test data, tables, and graphs.

Map Showing Quaternary Geology and Geomorphology of the Granite Park Area, Grand Canyon, Arizona

USGS Publications Warehouse

Hereford, Richard; Burke, Kelly J.; Thompson, Kathryn S.

2000-01-01

View to west-northwest showing map area and setting of Granite Park; Grand Canyon, Arizona. The Colorado River flows from right to left. Granite Park Wash is the light-colored area in foreground of photograph. The debris fan of 209 Mile Canyon is at left center. Pleistocene gravel is exposed in the steep, light-colored bank above 209 Mile Rapids at left edge of photograph. The black-colored ledge that forms the dark cliff at upper right of photograph is the basalt flow of Hamblin (1994). Sand dunes, debris fans, and terraces of the Colorado River cover the lower half of this area shown in this photograph.

Membrane catalyst layer for fuel cells

DOEpatents

Wilson, Mahlon S.

1993-01-01

A gas reaction fuel cell incorporates a thin catalyst layer between a solid polymer electrolyte (SPE) membrane and a porous electrode backing. The catalyst layer is preferably less than about 10 .mu.m in thickness with a carbon supported platinum catalyst loading less than about 0.35 mgPt/cm.sup.2. The film is formed as an ink that is spread and cured on a film release blank. The cured film is then transferred to the SPE membrane and hot pressed into the surface to form a catalyst layer having a controlled thickness and catalyst distribution. Alternatively, the catalyst layer is formed by applying a Na.sup.+ form of a perfluorosulfonate ionomer directly to the membrane, drying the film at a high temperature, and then converting the film back to the protonated form of the ionomer. The layer has adequate gas permeability so that cell performance is not affected and has a density and particle distribution effective to optimize proton access to the catalyst and electronic continuity for electron flow from the half-cell reaction occurring at the catalyst.

Oxidative coupling of methane using inorganic membrane reactor

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

Ma, Y.H.; Moser, W.R.; Dixon, A.G.

1995-12-31

The goal of this research is to improve the oxidative coupling of methane in a catalytic inorganic membrane reactor. A specific target is to achieve conversion of methane to C{sub 2} hydrocarbons at very high selectivity and relatively higher yields than in fixed bed reactors by controlling the oxygen supply through the membrane. A membrane reactor has the advantage of precisely controlling the rate of delivery of oxygen to the catalyst. This facility permits balancing the rate of oxidation and reduction of the catalyst. In addition, membrane reactors minimize the concentration of gas phase oxygen thus reducing non selective gasmore » phase reactions, which are believed to be a main route for formation of CO{sub x} products. Such gas phase reactions are a cause for decreased selectivity in oxidative coupling of methane in conventional flow reactors. Membrane reactors could also produce higher product yields by providing better distribution of the reactant gases over the catalyst than the conventional plug flow reactors. Modeling work which aimed at predicting the observed experimental trends in porous membrane reactors was also undertaken in this research program.« less

Integrated current collector and catalyst support

DOEpatents

Bregoli, Lawrence J.

1985-10-22

An integrated current collecting electrode for a molten carbonate fuel cell includes a corrugated metal conductive strip positioned in contact with a catalyst layer. The corrugations of the metal strip form a plurality of gas channels immediately adjacent the surface of the catalyst through which a reactant gas flows. Each channel is filled with a particulate material to maintain separation between the metal strip and the catalyst in ensuring gas channel integrity. The catalyst may be in the form of a compacted, particulate material provided the particle size of the material within the gas channels is larger than that of the catalyst particles to prevent catalyst migration to the metal conductor and provide reactant gas access to the catalyst layer. The gas channels formed by the corrugations of the metal strip are arranged in an offset pattern along the direction of gas flow for improved reactant gas distribution to the catalyst layer. The particulate material positioned within the gas flow channels may be a ceramic conductor such as a perovskite or a spinel for enhanced current collection.

Integrated current collector and catalyst support

DOEpatents

Bregoli, L.J.

1984-10-17

An integrated current collecting electrode for a molten carbonate fuel cell includes a corrugated metal conductive strip positioned in contact with a catalyst layer. The corrugations of the metal strip form a plurality of gas channels immediately adjacent the surface of the catalyst through which a reactant gas flows. Each channel is filled with a particulate material to maintain separation between the metal strip and the catalyst in ensuring gas channel integrity. The catalyst may be in the form of a compacted, particulate material provided the particle size of the material within the gas channels is larger than that of the catalyst particles to prevent catalyst migration to the metal conductor and provide reactant gas access to the catalyst layer. The gas channels formed by the corrugations of the metal strip are arranged in an offset pattern along the direction of gas flow for improved reactant gas distribution to the catalyst layer. The particulate material positioned within the gas flow channels may be a ceramic conductor such as a perovskite or a spinel for enhanced current collection.

Au-assisted fabrication of nano-holes on c-plane sapphire via thermal treatment guided by Au nanoparticles as catalysts

NASA Astrophysics Data System (ADS)

Sui, Mao; Pandey, Puran; Li, Ming-Yu; Zhang, Quanzhen; Kunwar, Sundar; Lee, Jihoon

2017-01-01

Nanoscale patterning of sapphires is a challenging task due to the high mechanical strength, chemical stability as well as thermal durability. In this paper, we demonstrate a gold droplet assisted approach of nano-hole fabrication on c-plane sapphire via a thermal treatment. Uniformly distributed nano-holes are fabricated on the sapphire surface guided by dome shaped Au nanoparticles (NPs) as catalysts and the patterning process is discussed based on the disequilibrium of vapor, liquid, solid interface energies at the Au NP/sapphire interface induced by the Au evaporation at high temperature. Followed by the re-equilibration of interface energy, transport of alumina from the beneath of NPs to the sapphire surface can occur along the NP/sapphire interface resulting in the formation of nano-holes. The fabrication of nano-holes using Au NPs as catalysts is a flexible, economical and convenient approach and can find applications in various optoelectronics.

Structure and catalytic activities of ferrous centers confined on the interface between carbon nanotubes and humic acid

NASA Astrophysics Data System (ADS)

Wang, Bing; Zhou, Xiaoyan; Wang, Dongqi; Yin, Jun-Jie; Chen, Hanqing; Gao, Xingfa; Zhang, Jing; Ibrahim, Kurash; Chai, Zhifang; Feng, Weiyue; Zhao, Yuliang

2015-01-01

Preparation of heterogeneous catalysts with active ferrous centers is of great significance for industrial and environmental catalytic processes. Nanostructured carbon materials (NCM), which possess free-flowing π electrons, can coordinate with transition metals, provide a confinement environment for catalysis, and act as potential supports or ligands to construct analogous complexes. However, designing such catalysts using NCM is still seldom studied to date. Herein, we synthesized a sandwich structured ternary complex via the coordination of Fe-loaded humic acid (HA) with C&z.dbd;C bonds in the aromatic rings of carbon nanotubes (CNTs), in which the O/N-Fe-C interface configuration provides the confinement environment for the ferrous sites. The experimental and theoretical results revealed octahedrally/tetrahedrally coordinated geometry at Fe centers, and the strong hybridization between CNT C π* and Fe 3d orbitals induces discretization of the atomic charges on aromatic rings of CNTs, which facilitates O2 adsorption and electron transfer from carbon to O2, which enhances O2 activation. The O2 activation by the novel HA/Fe-CNT complex can be applied in the oxidative degradation of phenol red (PR) and bisphenol A (BPA) in aqueous media.Preparation of heterogeneous catalysts with active ferrous centers is of great significance for industrial and environmental catalytic processes. Nanostructured carbon materials (NCM), which possess free-flowing π electrons, can coordinate with transition metals, provide a confinement environment for catalysis, and act as potential supports or ligands to construct analogous complexes. However, designing such catalysts using NCM is still seldom studied to date. Herein, we synthesized a sandwich structured ternary complex via the coordination of Fe-loaded humic acid (HA) with C&z.dbd;C bonds in the aromatic rings of carbon nanotubes (CNTs), in which the O/N-Fe-C interface configuration provides the confinement environment for the ferrous sites. The experimental and theoretical results revealed octahedrally/tetrahedrally coordinated geometry at Fe centers, and the strong hybridization between CNT C π* and Fe 3d orbitals induces discretization of the atomic charges on aromatic rings of CNTs, which facilitates O2 adsorption and electron transfer from carbon to O2, which enhances O2 activation. The O2 activation by the novel HA/Fe-CNT complex can be applied in the oxidative degradation of phenol red (PR) and bisphenol A (BPA) in aqueous media. Electronic supplementary information (ESI) available: Optimization of the mass ratios of HA to CNTs and the reaction pH conditions for Fe loading; scanning electron microscope (SEM), UV-Vis-near-infrared, Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR) for CNT-HA; EPR experiment and UPLC-ESI-MS analysis; and DFT calculation. See DOI: 10.1039/c4nr06665k

Talk Me off the Ledge: Surviving Solo Librarianship

ERIC Educational Resources Information Center

Karabush, Cynthia; Pleviak, Pam

2011-01-01

Solo school librarians are the air traffic controllers of the library world, serving hundreds, if not thousands, of students. They are responsible for a book budget, technology resources, orientation and research classes, book talks, and reading promotions, as well as professional development for teachers, guiding them in effective integration of…

Seismic Monitoring of Rock Falls in Yosemite National Park

NASA Astrophysics Data System (ADS)

Zimmer, V. L.; Stock, G. M.; Sitar, N.

2008-12-01

Between 1857 and 2007, more than 600 landslide events have been documented in Yosemite National Park, with the vast majority of events occurring as rock falls in Yosemite Valley. The conditions leading to and triggering rock fall are understood in approximately 50 percent of cases, but in the other 50 percent, there were no apparent triggers. Occasionally, large rock falls have been preceded by smaller events that, in retrospect, may have been precursors. Close range seismic monitoring presents an opportunity to study the conditions leading up to rock fall, as well as the mechanics of the actual rock fall as recorded seismically. During the winter of 2007-08, we conducted a rock fall seismic monitoring feasibility study in Yosemite Valley. A station consisting of an 8 Hz geophone and an accelerometer was placed on a ledge 1000 feet above the valley floor, in a historically active rock fall area known as the Three Brothers. At least two rock falls in this area were recorded by the instrumentation and witnessed by visitors, representing the first time rock falls have been recorded with seismic instrumentation in Yosemite Valley. Significant energy was recorded in a wide frequency range, from a few Hz to approximately 150 Hz, limited by the geophone response and attenuation of the signal due to distance to the source (400 m). Furthermore, there exists a weak signal approximately 5-10 seconds before the obvious rock fall signature. We hypothesize that the weak signal represents rock fall initiation manifesting as the first blocks sliding down the cliff face, while the stronger impulses represent these blocks impacting ledges and the bottom talus field. This study demonstrated that rock fall monitoring is feasible with seismic instrumentation, and serves as the catalyst for future studies using a network of sensors for more advanced analysis.

Modelling heterogeneous interfaces for solar water splitting

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

Pham, Tuan Anh; Ping, Yuan; Galli, Giulia

2017-01-09

The generation of hydrogen from water and sunlight others a promising approach for producing scalable and sustainable carbon-free energy. The key of a successful solar-to-fuel technology is the design of efficient, long-lasting and low-cost photoelectrochemical cells, which are responsible for absorbing sunlight and driving water splitting reactions. To this end, a detailed understanding and control of heterogeneous interfaces between photoabsorbers, electrolytes and catalysts present in photoelectrochemical cells is essential. Here we review recent progress and open challenges in predicting physicochemical properties of heterogeneous interfaces for solar water splitting applications using first-principles-based approaches, and highlights the key role of these calculationsmore » in interpreting increasingly complex experiments.« less

A comparative parametric study of a catalytic plate methane reformer coated with segmented and continuous layers of combustion catalyst for hydrogen production

NASA Astrophysics Data System (ADS)

Mundhwa, Mayur; Parmar, Rajesh D.; Thurgood, Christopher P.

2017-03-01

A parametric comparison study is carried out between segmented and conventional continuous layer configurations of the coated combustion-catalyst to investigate their influence on the performance of methane steam reforming (MSR) for hydrogen production in a catalytic plate reactor (CPR). MSR is simulated on one side of a thin plate over a continuous layer of nickel-alumina catalyst by implementing an experimentally validated surface microkinetic model. Required thermal energy for the MSR reaction is supplied by simulating catalytic methane combustion (CMC) on the opposite side of the plate over segmented and continuous layer of a platinum-alumina catalyst by implementing power law rate model. The simulation results of both coating configurations of the combustion-catalyst are compared using the following parameters: (1) co-flow and counter-flow modes between CMC and MSR, (2) gas hourly space velocity and (3) reforming-catalyst thickness. The study explains why CPR designed with the segmented combustion-catalyst and co-flow mode shows superior performance not only in terms of high hydrogen production but also in terms of minimizing the maximum reactor plate temperature and thermal hot-spots. The study shows that the segmented coating requires 7% to 8% less combustion-side feed flow and 70% less combustion-catalyst to produce the required flow of hydrogen (29.80 mol/h) on the reforming-side to feed a 1 kW fuel-cell compared to the conventional continuous coating of the combustion-catalyst.

Nanocrystal assembly for tandem catalysis

DOEpatents

Yang, Peidong; Somorjai, Gabor; Yamada, Yusuke; Tsung, Chia-Kuang; Huang, Wenyu

2014-10-14

The present invention provides a nanocrystal tandem catalyst comprising at least two metal-metal oxide interfaces for the catalysis of sequential reactions. One embodiment utilizes a nanocrystal bilayer structure formed by assembling sub-10 nm platinum and cerium oxide nanocube monolayers on a silica substrate. The two distinct metal-metal oxide interfaces, CeO.sub.2--Pt and Pt--SiO.sub.2, can be used to catalyze two distinct sequential reactions. The CeO.sub.2--Pt interface catalyzed methanol decomposition to produce CO and H.sub.2, which were then subsequently used for ethylene hydroformylation catalyzed by the nearby Pt--SiO.sub.2 interface. Consequently, propanal was selectively produced on this nanocrystal bilayer tandem catalyst.

Precipitation Behavior of Nanometer-Sized Carbides in a Nb-Ti-Bearing Low-Carbon Steel

NASA Astrophysics Data System (ADS)

Xiaolin, Li; Zhaodong, Wang; Xiangtao, Deng; Yong, Yang; Dan, Song; Guodong, Wang

The microstructure, mechanical property and precipitation behavior in a low carbon Nb-Ti micro-alloyed steel were investigated using dilatometer, optical microscopy and transmission electron microscope. The results show that the microstructure of the experimental steel treated by isothermal quenching process mainly consists of ferrite and martensite. The volume fraction of ferrite increases with a decrease in the isothermal temperature. It is found that both of interphase precipitation and supersaturated precipitation would appear in the samples treated by isothermal quenching process. Along with the isothermal temperature decreasing, the precipitation state changes from interphase precipitation to supersaturated precipitation. The interphase precipitation of these carbides with different row spacing and different orientation in ferrite grains, is related to the mobility of interfaces during γ/α transformation based on ledge mechanism. In addition to {110}α plane suggested by the ledge mechanism, the planar sheets of interphase precipitation are also found to be parallel with{035}a planes. Moreover, the interphase precipitation carbides were identified to have a NaCl-type crystal structure with a lattice parameter of 0.432 nm and obey the Baker-Nutting (B-N) orientation relationship with respect to ferrite matrix. The contribution of the precipitation hardening to the yield strength of the experiment steel has been estimated to be 337 MPa at 620 °C, based on Orowan mechanism.

Fabrication of High Performing PEMFC Catalyst-Coated Membranes with a Low Cost Air-Assisted Cylindrical Liquid Jets Spraying System

DOE PAGES

Peng, Xiong; Omasta, Travis; Rigdon, William; ...

2016-11-15

In this paper, a low cost air-assisted cylindrical liquid jets spraying (ACLJS) system was developed to prepare high-performance catalyst-coated membranes (CCMs) for proton exchange membrane fuel cells (PEMFCs). The catalyst ink was flowed from a cylindrical orifice and was atomized by an air stream fed from a coaxial slit and sprayed directly onto the membrane, which was suctioned to a heated aluminum vacuum plate. The CCM pore architecture including size, distribution and volume can be controlled using various flow parameters, and the impact of spraying conditions on electrode structure and PEMFC performance was investigated. CCMs fabricated in the fiber-type break-upmore » regime by ACLJS achieved very high performance during PEMFC testing, with the top-performing cells having a current density greater than 1900 mA/cm 2 at 0.7 V under H 2/O 2 flows and 700 mA/cm 2 under H 2/Air at 1.5 bar(absolute) pressure and 60% gas RH, and 80°C cell temperature.« less

Fabrication of High Performing PEMFC Catalyst-Coated Membranes with a Low Cost Air-Assisted Cylindrical Liquid Jets Spraying System

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

Peng, Xiong; Omasta, Travis; Rigdon, William

In this paper, a low cost air-assisted cylindrical liquid jets spraying (ACLJS) system was developed to prepare high-performance catalyst-coated membranes (CCMs) for proton exchange membrane fuel cells (PEMFCs). The catalyst ink was flowed from a cylindrical orifice and was atomized by an air stream fed from a coaxial slit and sprayed directly onto the membrane, which was suctioned to a heated aluminum vacuum plate. The CCM pore architecture including size, distribution and volume can be controlled using various flow parameters, and the impact of spraying conditions on electrode structure and PEMFC performance was investigated. CCMs fabricated in the fiber-type break-upmore » regime by ACLJS achieved very high performance during PEMFC testing, with the top-performing cells having a current density greater than 1900 mA/cm 2 at 0.7 V under H 2/O 2 flows and 700 mA/cm 2 under H 2/Air at 1.5 bar(absolute) pressure and 60% gas RH, and 80°C cell temperature.« less

PEROXIDE DESTRUCTION TESTING FOR THE 200 AREA EFFLUENT TREATMENT FACILITY

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

HALGREN DL

2010-03-12

The hydrogen peroxide decomposer columns at the 200 Area Effluent Treatment Facility (ETF) have been taken out of service due to ongoing problems with particulate fines and poor destruction performance from the granular activated carbon (GAC) used in the columns. An alternative search was initiated and led to bench scale testing and then pilot scale testing. Based on the bench scale testing three manganese dioxide based catalysts were evaluated in the peroxide destruction pilot column installed at the 300 Area Treated Effluent Disposal Facility. The ten inch diameter, nine foot tall, clear polyvinyl chloride (PVC) column allowed for the samemore » six foot catalyst bed depth as is in the existing ETF system. The flow rate to the column was controlled to evaluate the performance at the same superficial velocity (gpm/ft{sup 2}) as the full scale design flow and normal process flow. Each catalyst was evaluated on peroxide destruction performance and particulate fines capacity and carryover. Peroxide destruction was measured by hydrogen peroxide concentration analysis of samples taken before and after the column. The presence of fines in the column headspace and the discharge from carryover was generally assessed by visual observation. All three catalysts met the peroxide destruction criteria by achieving hydrogen peroxide discharge concentrations of less than 0.5 mg/L at the design flow with inlet peroxide concentrations greater than 100 mg/L. The Sud-Chemie T-2525 catalyst was markedly better in the minimization of fines and particle carryover. It is anticipated the T-2525 can be installed as a direct replacement for the GAC in the peroxide decomposer columns. Based on the results of the peroxide method development work the recommendation is to purchase the T-2525 catalyst and initially load one of the ETF decomposer columns for full scale testing.« less

Control of Meridional Flow by a Non-Uniform Rotational Magnetic Field

NASA Technical Reports Server (NTRS)

Mazuruk, Konstantin; Ramachandran, Narayanan

1999-01-01

The diffusive mass transfer of species during crystal growth in vertical ampoules is significantly affected by fluid flow in the liquid mother phase (melt). For electrically conductive melts, an elegant way of remotely inducing and controlling this flow is by utilizing a uniform rotational magnetic field (RMF) in the transverse direction. It induces an azimuthal flow which tends to homogenize the thermal and solutal fields. The rotating field also reduces the diffusion boundary layer, stabilizes temperature fluctuations, and promotes better overall crystal growth. For moderate strengths of the applied magnetic field (2-20 m Tesla) with frequencies of up to 400 Hz, the induced secondary meridional flow becomes significant. It typically consists of one roll at the bottom of the liquid column and a second roll (vortex) at the top. The flow along the centerline (ampoule axis) is directed from the growing solid (interface) towards the liquid (melt). In case of convex interfaces (e.g. in floating zone crystal growth) such flow behavior is beneficial since it suppresses diffusion at the center. However, for concave interfaces (e.g. vertical Bridgman crystal growth) such a flow tends to exacerbate the situation in making the interface shape more concave. It would be beneficial to have some control of this meridional flow- for example, a single recirculating cell with controllable direction and flow magnitude will make this technique even more attractive for crystal growth. Such flow control is a possibility if a non-uniform PNE field is utilized for this purpose. Although this idea has been proposed earlier, it has not been conclusively demonstrated so far. In this work, we derive the governing equations for the fluid dynamics for such a system and obtain solutions for a few important cases. Results from parallel experimental measurements of fluid flow in a mercury column subjected to non-uniform RMF will also be presented.

Photoreactor with self-contained photocatalyst recapture

DOEpatents

Gering, Kevin L.

2004-12-07

A system for the continuous use and recapture of a catalyst in liquid, comprising: a generally vertical reactor having a reaction zone with generally downwardly flowing liquid, and a catalyst recovery chamber adjacent the reaction zone containing a catalyst consisting of buoyant particles. The liquid in the reaction zone flows downward at a rate which exceeds the speed of upward buoyant migration of catalyst particles in the liquid, whereby catalyst particles introduced into the liquid in the reaction zone are drawn downward with the liquid. A slow flow velocity flotation chamber disposed below the reaction zone is configured to recapture the catalyst particles and allow them to float back into the catalyst recovery chamber for recycling into the reaction zone, rather than being swept downstream. A novel 3-dimensionally adjustable solar reflector directs light into the reaction zone to induce desired photocatalytic reactions within the liquid in the reaction zone.

75 FR 59078 - Safety Zone; Ledge Removal Project, Bass Harbor, ME

Federal Register 2010, 2011, 2012, 2013, 2014

2010-09-27

... DEPARTMENT OF HOMELAND SECURITY Coast Guard 33 CFR Part 165 [Docket No. USCG-2010-0806] RIN 1625-AA00 Safety Zone; Ledge Removal Project, Bass Harbor, ME AGENCY: Coast Guard, DHS. ACTION: Temporary... District USACE Web site: http://www.nae.usace.army.mil/projects/me/bassharbor/bassharbor.htm . No...

Track with overlapping links for dry coal extrusion pumps

DOEpatents

Saunders, Timothy; Brady, John D

2014-01-21

A chain for a particulate material extrusion pump includes a plurality of links, each of the plurality of links having a link body and a link ledge, wherein each link ledge of the plurality of links at least partially overlaps the link body of an adjacent one of the plurality of links.

Command module/service module reaction control subsystem assessment

NASA Technical Reports Server (NTRS)

Weary, D. P.

1971-01-01

Detailed review of component failure histories, qualification adequacy, manufacturing flow, checkout requirements and flow, ground support equipment interfaces, subsystem interface verification, protective devices, and component design did not reveal major weaknesses in the command service module (CSM) reaction control system (RCS). No changes to the CSM RCS were recommended. The assessment reaffirmed the adequacy of the CSM RCS for future Apollo missions.

Oxygen-promoted catalyst sintering influences number density, alignment, and wall number of vertically aligned carbon nanotubes

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

Shi, Wenbo; Li, Jinjing; Polsen, Erik S.

A lack of synthetic control and reproducibility during vertically aligned carbon nanotube (CNT) synthesis has stifled many promising applications of organic nanomaterials. Oxygen-containing species are particularly precarious in that they have both beneficial and deleterious effects and are notoriously difficult to control. In this paper, we demonstrated diatomic oxygen's ability, independent of water, to tune oxide-supported catalyst thin film dewetting and influence nanoscale (diameter and wall number) and macro-scale (alignment and density) properties for as-grown vertically aligned CNTs. In particular, single- or few-walled CNT forests were achieved at very low oxygen loading, with single-to-multi-walled CNT diameters ranging from 4.8 ±more » 1.3 nm to 6.4 ± 1.1 nm over 0–800 ppm O 2, and an expected variation in alignment, where both were related to the annealed catalyst morphology. Morphological differences were not the result of subsurface diffusion, but instead occurred via Ostwald ripening under several hundred ppm O 2, and this effect was mitigated by high H 2 concentrations and not due to water vapor (as confirmed in O 2-free water addition experiments), supporting the importance of O 2 specifically. Further characterization of the interface between the Fe catalyst and Al 2O 3 support revealed that either oxygen-deficit metal oxide or oxygen-adsorption on metals could be functional mechanisms for the observed catalyst nanoparticle evolution. Finally, taken as a whole, our results suggest that the impacts of O 2 and H 2 on the catalyst evolution have been underappreciated and underleveraged in CNT synthesis, and these could present a route toward facile manipulation of CNT forest morphology through control of the reactive gaseous atmosphere alone.« less

Oxygen-promoted catalyst sintering influences number density, alignment, and wall number of vertically aligned carbon nanotubes.

PubMed

Shi, Wenbo; Li, Jinjing; Polsen, Erik S; Oliver, C Ryan; Zhao, Yikun; Meshot, Eric R; Barclay, Michael; Fairbrother, D Howard; Hart, A John; Plata, Desiree L

2017-04-20

A lack of synthetic control and reproducibility during vertically aligned carbon nanotube (CNT) synthesis has stifled many promising applications of organic nanomaterials. Oxygen-containing species are particularly precarious in that they have both beneficial and deleterious effects and are notoriously difficult to control. Here, we demonstrated diatomic oxygen's ability, independent of water, to tune oxide-supported catalyst thin film dewetting and influence nanoscale (diameter and wall number) and macro-scale (alignment and density) properties for as-grown vertically aligned CNTs. In particular, single- or few-walled CNT forests were achieved at very low oxygen loading, with single-to-multi-walled CNT diameters ranging from 4.8 ± 1.3 nm to 6.4 ± 1.1 nm over 0-800 ppm O 2 , and an expected variation in alignment, where both were related to the annealed catalyst morphology. Morphological differences were not the result of subsurface diffusion, but instead occurred via Ostwald ripening under several hundred ppm O 2 , and this effect was mitigated by high H 2 concentrations and not due to water vapor (as confirmed in O 2 -free water addition experiments), supporting the importance of O 2 specifically. Further characterization of the interface between the Fe catalyst and Al 2 O 3 support revealed that either oxygen-deficit metal oxide or oxygen-adsorption on metals could be functional mechanisms for the observed catalyst nanoparticle evolution. Taken as a whole, our results suggest that the impacts of O 2 and H 2 on the catalyst evolution have been underappreciated and underleveraged in CNT synthesis, and these could present a route toward facile manipulation of CNT forest morphology through control of the reactive gaseous atmosphere alone.

Oxygen-promoted catalyst sintering influences number density, alignment, and wall number of vertically aligned carbon nanotubes

DOE PAGES

Shi, Wenbo; Li, Jinjing; Polsen, Erik S.; ...

2017-04-11

A lack of synthetic control and reproducibility during vertically aligned carbon nanotube (CNT) synthesis has stifled many promising applications of organic nanomaterials. Oxygen-containing species are particularly precarious in that they have both beneficial and deleterious effects and are notoriously difficult to control. In this paper, we demonstrated diatomic oxygen's ability, independent of water, to tune oxide-supported catalyst thin film dewetting and influence nanoscale (diameter and wall number) and macro-scale (alignment and density) properties for as-grown vertically aligned CNTs. In particular, single- or few-walled CNT forests were achieved at very low oxygen loading, with single-to-multi-walled CNT diameters ranging from 4.8 ±more » 1.3 nm to 6.4 ± 1.1 nm over 0–800 ppm O 2, and an expected variation in alignment, where both were related to the annealed catalyst morphology. Morphological differences were not the result of subsurface diffusion, but instead occurred via Ostwald ripening under several hundred ppm O 2, and this effect was mitigated by high H 2 concentrations and not due to water vapor (as confirmed in O 2-free water addition experiments), supporting the importance of O 2 specifically. Further characterization of the interface between the Fe catalyst and Al 2O 3 support revealed that either oxygen-deficit metal oxide or oxygen-adsorption on metals could be functional mechanisms for the observed catalyst nanoparticle evolution. Finally, taken as a whole, our results suggest that the impacts of O 2 and H 2 on the catalyst evolution have been underappreciated and underleveraged in CNT synthesis, and these could present a route toward facile manipulation of CNT forest morphology through control of the reactive gaseous atmosphere alone.« less

K- and L-edge X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) determination of differential orbital covalency (DOC) of transition metal sites

DOE PAGES

Baker, Michael L.; Mara, Michael W.; Yan, James J.; ...

2017-02-09

Continual advancements in the development of synchrotron radiation sources have resulted in X-ray based spectroscopic techniques capable of probing the electronic and structural properties of numerous systems. This review gives an overview of the application of metal K-edge and L-edge X-ray absorption spectroscopy (XAS), as well as Kα resonant inelastic X-ray scattering (RIXS), to the study of electronic structure in transition metal sites with emphasis on experimentally quantifying 3d orbital covalency. The specific sensitivities of K-edge XAS, L-edge XAS, and RIXS are discussed emphasizing the complementary nature of the methods. L-edge XAS and RIXS are sensitive to mixing between 3dmore » orbitals and ligand valence orbitals, and to the differential orbital covalency (DOC), that is, the difference in the covalencies for different symmetry sets of the d orbitals. Both L-edge XAS and RIXS are highly sensitive to and enable separation of σ and π donor bonding and π back bonding contributions to bonding. Applying ligand field multiplet simulations, including charge transfer via valence bond configuration interactions, DOC can be obtained for direct comparison with density functional theory calculations and to understand chemical trends. Here, the application of RIXS as a probe of frontier molecular orbitals in a heme enzyme demonstrates the potential of this method for the study of metal sites in highly covalent coordination sites in bioinorganic chemistry.« less

K- and L-edge X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) determination of differential orbital covalency (DOC) of transition metal sites

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

Baker, Michael L.; Mara, Michael W.; Yan, James J.

Continual advancements in the development of synchrotron radiation sources have resulted in X-ray based spectroscopic techniques capable of probing the electronic and structural properties of numerous systems. This review gives an overview of the application of metal K-edge and L-edge X-ray absorption spectroscopy (XAS), as well as Kα resonant inelastic X-ray scattering (RIXS), to the study of electronic structure in transition metal sites with emphasis on experimentally quantifying 3d orbital covalency. The specific sensitivities of K-edge XAS, L-edge XAS, and RIXS are discussed emphasizing the complementary nature of the methods. L-edge XAS and RIXS are sensitive to mixing between 3dmore » orbitals and ligand valence orbitals, and to the differential orbital covalency (DOC), that is, the difference in the covalencies for different symmetry sets of the d orbitals. Both L-edge XAS and RIXS are highly sensitive to and enable separation of σ and π donor bonding and π back bonding contributions to bonding. Applying ligand field multiplet simulations, including charge transfer via valence bond configuration interactions, DOC can be obtained for direct comparison with density functional theory calculations and to understand chemical trends. Here, the application of RIXS as a probe of frontier molecular orbitals in a heme enzyme demonstrates the potential of this method for the study of metal sites in highly covalent coordination sites in bioinorganic chemistry.« less

Clinical and Radiographic Evaluation of Procedural Errors during Preparation of Curved Root Canals with Hand and Rotary Instruments: A Randomized Clinical Study.

PubMed

Khanna, Rajesh; Handa, Aashish; Virk, Rupam Kaur; Ghai, Deepika; Handa, Rajni Sharma; Goel, Asim

2017-01-01

The process of cleaning and shaping the canal is not an easy goal to obtain, as canal curvature played a significant role during the instrumentation of the curved canals. The present in vivo study was conducted to evaluate procedural errors during the preparation of curved root canals using hand Nitiflex and rotary K3XF instruments. Procedural errors such as ledge formation, instrument separation, and perforation (apical, furcal, strip) were determined in sixty patients, divided into two groups. In Group I, thirty teeth in thirty patients were prepared using hand Nitiflex system, and in Group II, thirty teeth in thirty patients were prepared using K3XF rotary system. The evaluation was done clinically as well as radiographically. The results recorded from both groups were compiled and put to statistical analysis. Chi-square test was used to compare the procedural errors (instrument separation, ledge formation, and perforation). In the present study, both hand Nitiflex and rotary K3XF showed ledge formation and instrument separation. Although ledge formation and instrument separation by rotary K3XF file system was less as compared to hand Nitiflex. No perforation was seen in both the instrument groups. Canal curvature played a significant role during the instrumentation of the curved canals. Procedural errors such as ledge formation and instrument separation by rotary K3XF file system were less as compared to hand Nitiflex.

Clinical and Radiographic Evaluation of Procedural Errors during Preparation of Curved Root Canals with Hand and Rotary Instruments: A Randomized Clinical Study

PubMed Central

Khanna, Rajesh; Handa, Aashish; Virk, Rupam Kaur; Ghai, Deepika; Handa, Rajni Sharma; Goel, Asim

2017-01-01

Background: The process of cleaning and shaping the canal is not an easy goal to obtain, as canal curvature played a significant role during the instrumentation of the curved canals. Aim: The present in vivo study was conducted to evaluate procedural errors during the preparation of curved root canals using hand Nitiflex and rotary K3XF instruments. Materials and Methods: Procedural errors such as ledge formation, instrument separation, and perforation (apical, furcal, strip) were determined in sixty patients, divided into two groups. In Group I, thirty teeth in thirty patients were prepared using hand Nitiflex system, and in Group II, thirty teeth in thirty patients were prepared using K3XF rotary system. The evaluation was done clinically as well as radiographically. The results recorded from both groups were compiled and put to statistical analysis. Statistical Analysis: Chi-square test was used to compare the procedural errors (instrument separation, ledge formation, and perforation). Results: In the present study, both hand Nitiflex and rotary K3XF showed ledge formation and instrument separation. Although ledge formation and instrument separation by rotary K3XF file system was less as compared to hand Nitiflex. No perforation was seen in both the instrument groups. Conclusion: Canal curvature played a significant role during the instrumentation of the curved canals. Procedural errors such as ledge formation and instrument separation by rotary K3XF file system were less as compared to hand Nitiflex. PMID:29042727

L-edge sum rule analysis on 3d transition metal sites: from d10 to d0 and towards application to extremely dilute metallo-enzymes.

PubMed

Wang, Hongxin; Friedrich, Stephan; Li, Lei; Mao, Ziliang; Ge, Pinghua; Balasubramanian, Mahalingam; Patil, Daulat S

2018-03-28

According to L-edge sum rules, the number of 3d vacancies at a transition metal site is directly proportional to the integrated intensity of the L-edge X-ray absorption spectrum (XAS) for the corresponding metal complex. In this study, the numbers of 3d holes are characterized quantitatively or semi-quantitatively for a series of manganese (Mn) and nickel (Ni) complexes, including the electron configurations 3d 10 → 3d 0 . In addition, extremely dilute (<0.1% wt/wt) Ni enzymes were examined by two different approaches: (1) by using a high resolution superconducting tunnel junction X-ray detector to obtain XAS spectra with a very high signal-to-noise ratio, especially in the non-variant edge jump region; and (2) by adding an inert tracer to the sample that provides a prominent spectral feature to replace the weak edge jump for intensity normalization. In this publication, we present for the first time: (1) L-edge sum rule analysis for a series of Mn and Ni complexes that include electron configurations from an open shell 3d 0 to a closed shell 3d 10 ; (2) a systematic analysis on the uncertainties, especially on that from the edge jump, which was missing in all previous reports; (3) a clearly-resolved edge jump between pre-L 3 and post-L 2 regions from an extremely dilute sample; (4) an evaluation of an alternative normalization standard for L-edge sum rule analysis. XAS from two copper (Cu) proteins measured using a conventional semiconductor X-ray detector are also repeated as bridges between Ni complexes and dilute Ni enzymes. The differences between measuring 1% Cu enzymes and measuring <0.1% Ni enzymes are compared and discussed. This study extends L-edge sum rule analysis to virtually any 3d metal complex and any dilute biological samples that contain 3d metals.

Three-dimensional analysis of flow-chemical interaction within a single square channel of a lean NO x trap catalyst.

PubMed

Fornarelli, Francesco; Dadduzio, Ruggiero; Torresi, Marco; Camporeale, Sergio Mario; Fortunato, Bernardo

2018-02-01

A fully 3D unsteady Computational Fluid Dynamics (CFD) approach coupled with heterogeneous reaction chemistry is presented in order to study the behavior of a single square channel as part of a Lean [Formula: see text] Traps. The reliability of the numerical tool has been validated against literature data considering only active BaO site. Even though the input/output performance of such catalyst has been well known, here the spatial distribution within a single channel is investigated in details. The square channel geometry influences the flow field and the catalyst performance being the flow velocity distribution on the cross section non homogeneous. The mutual interaction between the flow and the active catalyst walls influences the spatial distribution of the volumetric species. Low velocity regions near the square corners and transversal secondary flows are shown in several cross-sections along the streamwise direction at different instants. The results shed light on the three-dimensional characteristic of both the flow field and species distribution within a single square channel of the catalyst with respect to 0-1D approaches.

Catalytic cartridge SO.sub.3 decomposer

DOEpatents

Galloway, Terry R.

1982-01-01

A catalytic cartridge internally heated is utilized as a SO.sub.3 decomposer for thermochemical hydrogen production. The cartridge has two embodiments, a cross-flow cartridge and an axial flow cartridge. In the cross-flow cartridge, SO.sub.3 gas is flowed through a chamber and incident normally to a catalyst coated tube extending through the chamber, the catalyst coated tube being internally heated. In the axial-flow cartridge, SO.sub.3 gas is flowed through the annular space between concentric inner and outer cylindrical walls, the inner cylindrical wall being coated by a catalyst and being internally heated. The modular cartridge decomposer provides high thermal efficiency, high conversion efficiency, and increased safety.

Flow Control in a Compact Inlet

NASA Astrophysics Data System (ADS)

Vaccaro, John C.

2011-12-01

An experimental investigation of flow control, via various control jets actuators, was undertaken to eliminate separation and secondary flows in a compact inlet. The compact inlet studied was highly aggressive with a length-to-diameter ratio of 1.5. A brand new facility was designed and built to enable various actuation methodologies as well as multiple measurement techniques. Techniques included static surface pressure, total pressure, and stereoscopic particle image velocimetry. Experimental data were supplemented with numerical simulations courtesy of Prof. Kenneth Jansen, Dr. Onkar Sahni, and Yi Chen. The baseline flow field was found to be dominated by two massive separations and secondary flow structures. These secondary structures were present at the aerodynamic interface plane in the form of two counter-rotating vortices inducing upwash along centerline. A dominant shedding frequency of 350 Hz was measured both at the aerodynamic interface plane and along the lower surface of the inlet. Flow control experiments started utilizing a pair of control jets placed in streamwise locations where flow was found to separate. Tests were performed for a range of inlet Mach numbers from 0.2 to 0.44. Steady and unsteady static pressure measurements along the upper and lower walls of the duct were performed for various combinations of actuation. The parameters that were tested include the control jets momentum coefficient, their blowing ratio, the actuation frequency, as well as different combinations of jets. It was shown that using mass flux ratio as a criterion to define flow control is not sufficient, and one needs to provide both the momentum coefficient and the blowing ratio to quantify the flow control performance. A detailed study was undertaken on controlling the upstream separation point for an inlet Mach number of 0.44. Similar to the baseline flow field, the flow field associated with the activation of a two-dimensional control jet actuator was dominated by secondary flow structures. Unlike the baseline, these secondary flow structures produced downwash along the centerline. The formation of such structures was caused by the core flow stagnating on the lower surface near the aerodynamic interface plane. Using the two-dimensional steady jet resulted in an increase in the spanwise flow within the inlet and a reduction in the energy content of the 350 Hz shedding frequency. Unsteady forcing did not show much improvement over steady forcing for this configuration. A spanwise varying control jet and a hybrid Coanda jet / vortex generator jets were tested to reduce the three-dimensionality of the flow field. It was found that anytime the flow control method suppressed separation along the centerline, counter-rotating vortices existed in the lower corners of the aerodynamic interface plane.

Development of the Monolith Froth Reactor for Catalytic Wet Oxidation of CELSS Model Wastes

NASA Technical Reports Server (NTRS)

Fisher, John W.; Abraham, Martin

1993-01-01

The aqueous phase oxidation of acetic acid, used as a model compound for the treatment of CELSS (Controlled Ecological Life Support System) waste, was carried out in the monolith froth reactor which utilizes two-phase flow in the monolith channels. The catalytic oxidation of acetic acid was carried out over a Pt/Al2O3 catalyst at temperatures and pressures below the critical point of water. The effect of externally controllable parameters (temperature, liquid flow rate, distributor plate orifice size, pitch, and catalyst distance from the distributor plate) on the rate of acetic acid oxidation was investigated. Results indicate reaction rate increased with increasing temperature and exhibited a maximum with respect to liquid flow rate. The apparent activation energy calculated from reaction rate data was 99.7 kJ/mol. This value is similar to values reported for the oxidation of acetic acid in other systems and is comparable to intrinsic values calculated for oxidation reactions. The kinetic data were modeled using simple power law kinetics. The effect of "froth" feed system characteristics was also investigated. Results indicate that the reaction rate exhibits a maximum with respect to distributor plate orifice size, pitch, and catalyst distance from the distributor plate. Fundamental results obtained were used to extrapolate where the complete removal of acetic acid would be obtained and for the design and operation of a full scale CELSS treatment system.

5. View of remaining rock ledge from construction of passage ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

5. View of remaining rock ledge from construction of passage to enter mill (Riverdale Cotton Mill was built into the side of a hill). Partially subterranean area was popular with employees trying to escape the heat of the mill, now an unofficial smoking area. - Riverdale Cotton Mill, Corner of Middle & Lower Streets, Valley, Chambers County, AL

Controller and interface module for the High-Speed Data Acquisition System correlator/accumulator

NASA Technical Reports Server (NTRS)

Brokl, S. S.

1985-01-01

One complex channel of the High-Speed Data Acquisition System (a subsystem used in the Goldstone solar system radar), consisting of two correlator modules and one accumulator module, is operated by the controller and interface module interfaces are provided to the VAX UNIBUS for computer control, monitor, and test of the controller and correlator/accumulator. The correlator and accumulator modules controlled by this module are the key digital signal processing elements of the Goldstone High-Speed Data Acquisition System. This fully programmable unit provides for a wide variety of correlation and filtering functions operating on a three megaword/second data flow. Data flow is to the VAX by way of the I/O port of a FPS 5210 array processor.

Vibroconvective mixing applied to vertical Bridgman growth

NASA Astrophysics Data System (ADS)

Zawilski, Kevin T.; Claudia, M.; Custodio, C.; DeMattei, Robert C.; Feigelson, Robert S.

2003-10-01

A promising method for stirring melts during vertical Bridgman growth is the coupled vibrational stirring (CVS) method. It involves the application of low frequency vibrations to the outside of the growth ampoule and produces strong flows emanating from the fluid surface. Although the technique was pioneered a number of years ago, previous studies have not provided sufficient information to explain how to control CVS generated flows in a particular system. This paper examines both the fluid flow produced by CVS and the effect of these flows on a model oxide growth system. CVS generated flows were studied using tracer particles in a water/glycerin system. The particle velocities were measured as a function of distance from the fluid surface. A large velocity gradient, decreasing from the surface, was found to be present. The velocity profile produced was dependent on the vibrational amplitude and frequency, the crucible diameter, and the fluid viscosity. The effects of CVS flows on the crystal growth interface were studied using NaNO 3 as a model oxide. Under non-growth conditions (i.e. no furnace or crucible translation), the solid-liquid interface position was found to be a strong function of vibrational frequency once CVS generated flows approached the interface. During crystal growth, undesirable growth rate fluctuations were found as the growth interface moved into regions of increasing fluid flow. This data suggests that a control system in which CVS flows are continuously decreased during growth to maintain a constant flow rate in the vicinity of the growth interface is necessary in order to prevent or reduce growth rate fluctuations.

Multiple sample characterization of coals and other substances by controlled-atmosphere programmed temperature oxidation

DOEpatents

LaCount, Robert B.

1993-01-01

A furnace with two hot zones holds multiple analysis tubes. Each tube has a separable sample-packing section positioned in the first hot zone and a catalyst-packing section positioned in the second hot zone. A mass flow controller is connected to an inlet of each sample tube, and gas is supplied to the mass flow controller. Oxygen is supplied through a mass flow controller to each tube to either or both of an inlet of the first tube and an intermediate portion between the tube sections to intermingle with and oxidize the entrained gases evolved from the sample. Oxidation of those gases is completed in the catalyst in each second tube section. A thermocouple within a sample reduces furnace temperature when an exothermic condition is sensed within the sample. Oxidized gases flow from outlets of the tubes to individual gas cells. The cells are sequentially aligned with an infrared detector, which senses the composition and quantities of the gas components. Each elongated cell is tapered inward toward the center from cell windows at the ends. Volume is reduced from a conventional cell, while permitting maximum interaction of gas with the light beam. Reduced volume and angulation of the cell inlets provide rapid purgings of the cell, providing shorter cycles between detections. For coal and other high molecular weight samples, from 50% to 100% oxygen is introduced to the tubes.

Controllable synthesis of metal selenide heterostructures mediated by Ag2Se nanocrystals acting as catalysts.

PubMed

Zhou, Jiangcong; Huang, Feng; Xu, Ju; Wang, Yuansheng

2013-10-21

Ag2Se nanocrystals were demonstrated to be novel semiconductor mediators, or in other word catalysts, for the growth of semiconductor heterostructures in solution. This is a result of the unique feature of Ag2Se as a fast ion conductor, allowing foreign cations to dissolve and then to heterogrow the second phase. Using Ag2Se nanocrystals as catalysts, dimeric metal selenide heterostructures such as Ag2Se-CdSe and Ag2Se-ZnSe, and even multi-segment heterostructures such as Ag2Se-CdSe-ZnSe and Ag2Se-ZnSe-CdSe, were successfully synthesized. Several interesting features were found in the Ag2Se based heterogrowth. At the initial stage of heterogrowth, a layer of the second phase forms on the surface of an Ag2Se nanosphere, with a curved junction interface between the two phases. With further growth of the second phase, the Ag2Se nanosphere tends to flatten the junction surface by modifying its shape from sphere to hemisphere in order to minimize the conjunct area and thus the interfacial energy. Notably, the crystallographic relationship of the two phases in the heterostructure varies with the lattice parameters of the second phase, in order to reduce the lattice mismatch at the interface. Furthermore, a small lattice mismatch at the interface results in a straight rod-like second phase, while a large lattice mismatch would induce a tortuous product. The reported results may provide a new route for developing novel selenide semiconductor heterostructures which are potentially applicable in optoelectronic, biomedical, photovoltaic and catalytic fields.

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

Liu, Fang; Xie, Dong Yue; Majdi, Tahereh

By applying a simple and inexpensive thermal treatment, we synthesized supported gold-oxide nanostructures, which have potential applications to plasmonic devices and biosensors. The regrowth of nominally stable substrates under gold nanoparticles is associated with the appearance of preferential orientations of dewetted nanoparticles and the formation of atomically sharp interfacial monolayers. Steps present at the interfacial monolayer usually occur at defects including the intersection points of twin planes at the interface. They were related to the nucleation and immigration of the interfacial monolayers, prompting the substrate regrowth. Accordingly, we proposed the twin-assisted growth mechanism, which provides insight on the synthesis ofmore » gold-oxide nanostructures. - Highlights: • The twin-assisted growth mechanism is proposed for the abnormal regrowth of substrate underneath Au nanoparticles. • The substrate regrowth is related to the steps and ledges that are present at the Au–MgAl{sub 2}O{sub 4} interfacial monolayers. • Interfacial steps are detected at defects such as the intersecting points of twin planes at the interface.« less

Method of treating emissions of a hybrid vehicle with a hydrocarbon absorber and a catalyst bypass system

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

Roos, Bryan Nathaniel; Gonze, Eugene V; Santoso, Halim G

A method of treating emissions from an internal combustion engine of a hybrid vehicle includes directing a flow of air created by the internal combustion engine when the internal combustion engine is spinning but not being fueled through a hydrocarbon absorber to collect hydrocarbons within the flow of air. When the hydrocarbon absorber is full and unable to collect additional hydrocarbons, the flow of air is directed through an electrically heated catalyst to treat the flow of air and remove the hydrocarbons. When the hydrocarbon absorber is not full and able to collect additional hydrocarbons, the flow of air ismore » directed through a bypass path that bypasses the electrically heated catalyst to conserve the thermal energy stored within the electrically heated catalyst.« less

Six-flow operations for catalyst development in Fischer-Tropsch synthesis: Bridging the gap between high-throughput experimentation and extensive product evaluation

NASA Astrophysics Data System (ADS)

Sartipi, Sina; Jansma, Harrie; Bosma, Duco; Boshuizen, Bart; Makkee, Michiel; Gascon, Jorge; Kapteijn, Freek

2013-12-01

Design and operation of a "six-flow fixed-bed microreactor" setup for Fischer-Tropsch synthesis (FTS) is described. The unit consists of feed and mixing, flow division, reaction, separation, and analysis sections. The reactor system is made of five heating blocks with individual temperature controllers, assuring an identical isothermal zone of at least 10 cm along six fixed-bed microreactor inserts (4 mm inner diameter). Such a lab-scale setup allows running six experiments in parallel, under equal feed composition, reaction temperature, and conditions of separation and analysis equipment. It permits separate collection of wax and liquid samples (from each flow line), allowing operation with high productivities of C5+ hydrocarbons. The latter is crucial for a complete understanding of FTS product compositions and will represent an advantage over high-throughput setups with more than ten flows where such instrumental considerations lead to elevated equipment volume, cost, and operation complexity. The identical performance (of the six flows) under similar reaction conditions was assured by testing a same catalyst batch, loaded in all microreactors.

Static and dynamic structural characterization of nanomaterial catalysts

NASA Astrophysics Data System (ADS)

Masiel, Daniel Joseph

Heterogeneous catalysts systems are pervasive in industry, technology and academia. These systems often involve nanostructured transition metal particles that have crucial interfaces with either their supports or solid products. Understanding the nature of these interfaces as well as the structure of the catalysts and support materials themselves is crucial for the advancement of catalysis in general. Recent developments in the field of transmission electron microscopy (TEM) including dynamic transmission electron microscopy (DTEM), electron tomography, and in situ techniques stand poised to provide fresh insight into nanostructured catalyst systems. Several electron microscopy techniques are applied in this study to elucidate the mechanism of silica nanocoil growth and to discern the role of the support material and catalyst size in carbon dioxide and steam reforming of methane. The growth of silica nanocoils by faceted cobalt nanoparticles is a process that was initially believed to take place via a vapor-liquid-solid growth mechanism similar to other nanowire growth techniques. The extensive TEM work described here suggests that the process may instead occur via transport of silicate and silica species over the nanoparticle surface. Electron tomography studies of the interface between the catalyst particles and the wire indicate that they grow from edges between facets. Studies on reduction of the Co 3O4 nanoparticle precursors to the faceted pure cobalt catalysts were carried out using DTEM and in situ heating. Supported catalyst systems for methane reforming were studied using dark field scanning TEM to better understand sintering effects and the increased activity of Ni/Co catalysts supported by carbon nanotubes. Several novel electron microscopy techniques are described including annular dark field DTEM and a metaheuristic algorithm for solving the phase problem of coherent diffractive imaging. By inserting an annular dark field aperture into the back focal plane of the objective lens in a DTEM, time-resolved dark field images can be produced that have vastly improved contrast for supported catalyst materials compared to bright field DTEM imaging. A new algorithm called swarm optimized phase retrieval is described that uses a population-based approach to solve for the missing phases of diffraction data from discrete particles.

X-ray spectroscopy for chemistry in the 2-4 keV energy regime at the XMaS beamline: ionic liquids, Rh and Pd catalysts in gas and liquid environments, and Cl contamination in γ-Al2O3.

PubMed

Thompson, Paul B J; Nguyen, Bao N; Nicholls, Rachel; Bourne, Richard A; Brazier, John B; Lovelock, Kevin R J; Brown, Simon D; Wermeille, Didier; Bikondoa, Oier; Lucas, Christopher A; Hase, Thomas P A; Newton, Mark A

2015-11-01

The 2-4 keV energy range provides a rich window into many facets of materials science and chemistry. Within this window, P, S, Cl, K and Ca K-edges may be found along with the L-edges of industrially important elements from Y through to Sn. Yet, compared with those that cater for energies above ca. 4-5 keV, there are relatively few resources available for X-ray spectroscopy below these energies. In addition, in situ or operando studies become to varying degrees more challenging than at higher X-ray energies due to restrictions imposed by the lower energies of the X-rays upon the design and construction of appropriate sample environments. The XMaS beamline at the ESRF has recently made efforts to extend its operational energy range to include this softer end of the X-ray spectrum. In this report the resulting performance of this resource for X-ray spectroscopy is detailed with specific attention drawn to: understanding electrostatic and charge transfer effects at the S K-edge in ionic liquids; quantification of dilution limits at the Cl K- and Rh L3-edges and structural equilibria in solution; in vacuum deposition and reduction of [Rh(I)(CO)2Cl]2 to γ-Al2O3; contamination of γ-Al2O3 by Cl and its potential role in determining the chemical character of supported Rh catalysts; and the development of chlorinated Pd catalysts in `green' solvent systems. Sample environments thus far developed are also presented, characterized and their overall performance evaluated.

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

Catalytic process for control of NO.sub.x emissions using hydrogen

DOEpatents

Sobolevskiy, Anatoly; Rossin, Joseph A.; Knapke, Michael J.

2010-05-18

A selective catalytic reduction process with a palladium catalyst for reducing NOx in a gas, using hydrogen as a reducing agent. A zirconium sulfate (ZrO.sub.2)SO.sub.4 catalyst support material with about 0.01-2.0 wt. % Pd is applied to a catalytic bed positioned in a flow of exhaust gas at about 70-200.degree. C. The support material may be (ZrO.sub.2--SiO.sub.2)SO.sub.4. H.sub.2O and hydrogen may be injected into the exhaust gas upstream of the catalyst to a concentration of about 15-23 vol. % H.sub.2O and a molar ratio for H.sub.2/NO.sub.x in the range of 10-100. A hydrogen-containing fuel may be synthesized in an Integrated Gasification Combined Cycle power plant for combustion in a gas turbine to produce the exhaust gas flow. A portion of the fuel may be diverted for the hydrogen injection.

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

DOE PAGES

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

2016-10-01

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

Catalytic nanoporous membranes

DOEpatents

Pellin, Michael J; Hryn, John N; Elam, Jeffrey W

2013-08-27

A nanoporous catalytic membrane which displays several unique features Including pores which can go through the entire thickness of the membrane. The membrane has a higher catalytic and product selectivity than conventional catalysts. Anodic aluminum oxide (AAO) membranes serve as the catalyst substrate. This substrate is then subjected to Atomic Layer Deposition (ALD), which allows the controlled narrowing of the pores from 40 nm to 10 nm in the substrate by deposition of a preparatory material. Subsequent deposition of a catalytic layer on the inner surfaces of the pores reduces pore sizes to less than 10 nm and allows for a higher degree of reaction selectivity. The small pore sizes allow control over which molecules enter the pores, and the flow-through feature can allow for partial oxidation of reactant species as opposed to complete oxidation. A nanoporous separation membrane, produced by ALD is also provided for use in gaseous and liquid separations. The membrane has a high flow rate of material with 100% selectivity. Also provided is a method for producing a catalytic membrane having flow-through pores and discreet catalytic clusters adhering to the inside surfaces of the pores.

Performance enhancement of iron-chromium redox flow batteries by employing interdigitated flow fields

NASA Astrophysics Data System (ADS)

Zeng, Y. K.; Zhou, X. L.; Zeng, L.; Yan, X. H.; Zhao, T. S.

2016-09-01

The catalyst for the negative electrode of iron-chromium redox flow batteries (ICRFBs) is commonly prepared by adding a small amount of Bi3+ ions in the electrolyte and synchronously electrodepositing metallic particles onto the electrode surface at the beginning of charge process. Achieving a uniform catalyst distribution in the porous electrode, which is closely related to the flow field design, is critically important to improve the ICRFB performance. In this work, the effects of flow field designs on catalyst electrodeposition and battery performance are investigated. It is found that compared to the serpentine flow field (SFF) design, the interdigitated flow field (IFF) forces the electrolyte through the porous electrode between the neighboring channels and enhances species transport during the processes of both the catalyst electrodeposition and iron/chromium redox reactions, thus enabling a more uniform catalyst distribution and higher mass transport limitation. It is further demonstrated that the energy efficiency of the ICRFB with the IFF reaches 80.7% at a high current density (320 mA cm-2), which is 8.2% higher than that of the ICRFB with the SFF. With such a high performance and intrinsically low-cost active materials, the ICRFB with the IFF offers a great promise for large-scale energy storage.

Innovative Sol-Gel Routes for the Bottom-up Preparation of Heterogeneous Catalysts.

PubMed

Debecker, Damien P

2017-12-11

Heterogeneous catalysts can be prepared by different methods offering various levels of control on the final properties of the solid. In this account, we exemplify bottom-up preparation routes that are based on the sol-gel chemistry and allow to tailor some decisive properties of solid catalysts. First, an emulsion templating strategy is shown to lead to macrocellular self-standing monoliths with a macroscopic 3D structure. The latter can be used as catalyst or catalyst supports in flow chemistry, without requiring any subsequent shaping step. Second, the aerosol-assisted sol-gel process allows for the one-step and continuous production of porous mixed oxides. Tailored textural properties can be obtained together with an excellent control on composition and homogeneity. Third, the application of non-hydrolytic sol-gel routes, in the absence of water, leads to mixed oxides with outstanding textural properties and with peculiar surface chemistry. In all cases, the resulting catalytic performance can be correlated with the specificities of the preparation routes presented. This is exemplified in catalytic reactions in the fields of biomass conversion, petro chemistry, enantioselective organic synthesis, and air pollution mitigation. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Direct in Situ Measurement of Charge Transfer Processes During Photoelectrochemical Water Oxidation on Catalyzed Hematite

DOE PAGES

Qiu, Jingjing; Hajibabaei, Hamed; Nellist, Michael R.; ...

2017-08-17

Electrocatalysts improve the efficiency of light-absorbing semiconductor photoanodes driving the oxygen evolution reaction, but the precise function(s) of the electrocatalysts remains unclear. We directly measure, for the first time, the interface carrier transport properties of a prototypical visible-light-absorbing semiconductor, α-Fe 2O 3, in contact with one of the fastest known water oxidation catalysts, Ni 0.8Fe 0.2O x, by directly measuring/controlling the current and/or voltage at the Ni 0.8Fe 0.2O x catalyst layer using a second working electrode. The measurements demonstrate that the majority of photogenerated holes in α-Fe 2O 3 directly transfer to the catalyst film over a wide rangemore » of conditions and that the Ni 0.8Fe 0.2O x is oxidized by photoholes to an operating potential sufficient to drive water oxidation at rates that match the photocurrent generated by the α-Fe 2O 3. The Ni 0.8Fe 0.2O x therefore acts as both a hole-collecting contact and a catalyst for the photoelectrochemical water oxidation process. Separate measurements show that the illuminated junction photovoltage across the α-Fe 2O 3|Ni 0.8Fe 0.2O x interface is significantly decreased by the oxidation of Ni 2+ to Ni 3+ and the associated increase in the Ni 0.8Fe 0.2O x electrical conductivity. Finally, in sum, the results illustrate the underlying operative charge-transfer and photovoltage generation mechanisms of catalyzed photoelectrodes, thus guiding their continued improvement.« less

Direct liquid-feed fuel cell with membrane electrolyte and manufacturing thereof

NASA Technical Reports Server (NTRS)

Narayanan, Sekharipuram (Inventor); Surampudi, Subbarao (Inventor); Halpert, Gerald (Inventor)

1999-01-01

An improved direct liquid-feed fuel cell having a solid membrane electrolyte for electrochemical reactions of an organic fuel. Improvements in interfacing of the catalyst layer and the membrane and activating catalyst materials are disclosed.

Revealing the Bonding Environment of Zn in ALD Zn(O,S) Buffer Layers through X-ray Absorption Spectroscopy

PubMed Central

2017-01-01

Zn(O,S) buffer layer electronic configuration is determined by its composition and thickness, tunable through atomic layer deposition. The Zn K and L-edges in the X-ray absorption near edge structure verify ionicity and covalency changes with S content. A high intensity shoulder in the Zn K-edge indicates strong Zn 4s hybridized states and a preferred c-axis orientation. 2–3 nm thick films with low S content show a subdued shoulder showing less contribution from Zn 4s hybridization. A lower energy shift with film thickness suggests a decreasing bandgap. Further, ZnSO4 forms at substrate interfaces, which may be detrimental for device performance. PMID:29083141

Kinetic effects in InP nanowire growth and stacking fault formation: the role of interface roughening.

PubMed

Chiaramonte, Thalita; Tizei, Luiz H G; Ugarte, Daniel; Cotta, Mônica A

2011-05-11

InP nanowire polytypic growth was thoroughly studied using electron microscopy techniques as a function of the In precursor flow. The dominant InP crystal structure is wurtzite, and growth parameters determine the density of stacking faults (SF) and zinc blende segments along the nanowires (NWs). Our results show that SF formation in InP NWs cannot be univocally attributed to the droplet supersaturation, if we assume this variable to be proportional to the ex situ In atomic concentration at the catalyst particle. An imbalance between this concentration and the axial growth rate was detected for growth conditions associated with larger SF densities along the NWs, suggesting a different route of precursor incorporation at the triple phase line in that case. The formation of SFs can be further enhanced by varying the In supply during growth and is suppressed for small diameter NWs grown under the same conditions. We attribute the observed behaviors to kinetically driven roughening of the semiconductor/metal interface. The consequent deformation of the triple phase line increases the probability of a phase change at the growth interface in an effort to reach local minima of system interface and surface energy.

Electric field tuned MoS2/metal interface for hydrogen evolution catalyst from first-principles investigations

NASA Astrophysics Data System (ADS)

Ling, F. L.; Zhou, T. W.; Liu, X. Q.; Kang, W.; Zeng, W.; Zhang, Y. X.; Fang, L.; Lu, Y.; Zhou, M.

2018-01-01

Understanding the interfacial properties of catalyst/substrate is crucial for the design of high-performance catalyst for important chemical reactions. Recent years have witnessed a surge of research in utilizing MoS2 as a promising electro-catalyst for hydrogen production, and field effect has been employed to enhance the activity (Wang et al 2017 Adv. Mater. 29, 1604464; Yan et al 2017 Nano Lett. 17, 4109-15). However, the underlying atomic mechanism remains unclear. In this paper, by using the prototype MoS2/Au system as a probe, we investigate effects of external electric field on the interfacial electronic structures via density functional theory (DFT) based first-principles calculations. Our results reveal that although there is no covalent interaction between MoS2 overlayer and Au substrate, an applied electric field efficiently adjusts the charge transfer between MoS2 and Au, leading to tunable Schottky barrier type (n-type to p-type) and decrease of barrier height to facilitate charge injection. Furthermore, we predict that the adsorption energy of atomic hydrogen on MoS2/Au to be readily controlled by electric field to a broad range within a modest magnitude of field, which may benefit the performance enhancement of hydrogen evolution reaction. Our DFT results provide valuable insight into the experimental observations and pave the way for future understanding and control of catalysts in practice, such as those with vacancies, defects, edge states or synthesized nanostructures.

Safety Assessment of Two Hybrid Instrumentation Techniques in a Dental Student Endodontic Clinic: A Retrospective Study.

PubMed

Coelho, Marcelo Santos; Card, Steven John; Tawil, Peter Zahi

2017-03-01

The aim of this study was to retrospectively assess the safety potential of a hybrid technique combining nickel-titanium (NiTi) reciprocating and rotary instruments by third- and fourth-year dental students in the predoctoral endodontics clinic at one U.S. dental school. For the study, 3,194 root canal treatments performed by 317 dental students from 2012 through 2015 were evaluated for incidence of ledge creation and instrument separation. The hybrid reciprocating and rotary technique (RRT) consisted of a glide path creation with stainless steel hand files up to size 15/02, a crown down preparation with a NiTi reciprocating instrument, and an apical preparation with NiTi rotary instruments. The control was a traditional rotary and hand technique (RHT) that consisted of the same glide path procedure followed by a crown down preparation with NiTi rotary instruments and an apical preparation with NiTi hand instruments. The results showed that the RHT technique presented a rate of ledge creation of 1.4% per root and the RRT technique was 0.5% per root (p<0.05). Three stainless steel hand files separated: two in the RHT group and one in the RRT group. There was no separation of any NiTi file in any of the techniques. The use of the reciprocating and rotary technique for root canal instrumentation by these dental students provided good safety. This hybrid technique offered a low rate of ledge creation along with no NiTi instrument separation.

Free-surface flow of liquid oxygen under non-uniform magnetic field

NASA Astrophysics Data System (ADS)

Bao, Shi-Ran; Zhang, Rui-Ping; Wang, Kai; Zhi, Xiao-Qin; Qiu, Li-Min

2017-01-01

The paramagnetic property of oxygen makes it possible to control the two-phase flow at cryogenic temperatures by non-uniform magnetic fields. The free-surface flow of vapor-liquid oxygen in a rectangular channel was numerically studied using the two-dimensional phase field method. The effects of magnetic flux density and inlet velocity on the interface deformation, flow pattern and pressure drop were systematically revealed. The liquid level near the high-magnetic channel center was lifted upward by the inhomogeneous magnetic field. The interface height difference increased almost linearly with the magnetic force. For all inlet velocities, pressure drop under 0.25 T was reduced by 7-9% due to the expanded local cross-sectional area, compared to that without magnetic field. This work demonstrates the effectiveness of employing non-uniform magnetic field to control the free-surface flow of liquid oxygen. This non-contact method may be used for promoting the interface renewal, reducing the flow resistance, and improving the flow uniformity in the cryogenic distillation column, which may provide a potential for enhancing the operating efficiency of cryogenic air separation.

Save medical personnel's time by improved user interfaces.

PubMed

Kindler, H

1997-01-01

Common objectives in the industrial countries are the improvement of quality of care, clinical effectiveness, and cost control. Cost control, in particular, has been addressed through the introduction of case mix systems for reimbursement by social-security institutions. More data is required to enable quality improvement, increases in clinical effectiveness and for juridical reasons. At first glance, this documentation effort is contradictory to cost reduction. However, integrated services for resource management based on better documentation should help to reduce costs. The clerical effort for documentation should be decreased by providing a co-operative working environment for healthcare professionals applying sophisticated human-computer interface technology. Additional services, e.g., automatic report generation, increase the efficiency of healthcare personnel. Modelling the medical work flow forms an essential prerequisite for integrated resource management services and for co-operative user interfaces. A user interface aware of the work flow provides intelligent assistance by offering the appropriate tools at the right moment. Nowadays there is a trend to client/server systems with relational databases or object-oriented databases as repository. The work flows used for controlling purposes and to steer the user interfaces must be represented in the repository.

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

Rioux, Robert M.

In this work, we have primarily utilized isothermal titration calorimetry (ITC) and complimentary catalyst characterization techniques to study and assess the impact of solution conditions (i.e., solid-liquid) interface on the synthesis of heterogeneous and electro-catalysts. Isothermal titration calorimetry is well-known technique from biochemistry/physics, but has been applied to a far lesser extent to characterize buried solid-liquid interfaces in materials science. We demonstrate the utility and unique information provided by ITC for two distinct catalytic systems. We explored the thermodynamics associated catalyst synthesis for two systems: (i) ion-exchange or strong electrostatic adsorption for Pt and Pd salts on silica and aluminamore » materials (ii) adsorption to provide covalent attachment of metal and metal-oxo clusters to Dion-Jacobsen perovskite materials.« less

Systems and methods for rebalancing redox flow battery electrolytes

DOEpatents

Pham, Ai Quoc; Chang, On Kok

2015-03-17

Various methods of rebalancing electrolytes in a redox flow battery system include various systems using a catalyzed hydrogen rebalance cell configured to minimize the risk of dissolved catalyst negatively affecting flow battery performance. Some systems described herein reduce the chance of catalyst contamination of RFB electrolytes by employing a mediator solution to eliminate direct contact between the catalyzed membrane and the RFB electrolyte. Other methods use a rebalance cell chemistry that maintains the catalyzed electrode at a potential low enough to prevent the catalyst from dissolving.

L-edge sum rule analysis on 3d transition metal sites: from d 10 to d 0 and towards application to extremely dilute metallo-enzymes

DOE PAGES

Wang, Hongxin; Friedrich, Stephan; Li, Lei; ...

2018-02-13

According to L-edge sum rules, the number of 3d vacancies at a transition metal site is directly proportional to the integrated intensity of the L-edge X-ray absorption spectrum (XAS) for the corresponding metal complex. In this study, the numbers of 3d holes are characterized quantitatively or semi-quantitatively for a series of manganese (Mn) and nickel (Ni) complexes, including the electron configurations 3d 10 → 3d 0. In addition, extremely dilute (<0.1% wt/wt) Ni enzymes were examined by two different approaches: (1) by using a high resolution superconducting tunnel junction X-ray detector to obtain XAS spectra with a very high signal-to-noisemore » ratio, especially in the non-variant edge jump region; and (2) by adding an inert tracer to the sample that provides a prominent spectral feature to replace the weak edge jump for intensity normalization. In this publication, we present for the first time: (1) L-edge sum rule analysis for a series of Mn and Ni complexes that include electron configurations from an open shell 3d0 to a closed shell 3d 10; (2) a systematic analysis on the uncertainties, especially on that from the edge jump, which was missing in all previous reports; (3) a clearly-resolved edge jump between pre-L 3 and post-L 2 regions from an extremely dilute sample; (4) an evaluation of an alternative normalization standard for L-edge sum rule analysis. XAS from two copper (Cu) proteins measured using a conventional semiconductor X-ray detector are also repeated as bridges between Ni complexes and dilute Ni enzymes. The differences between measuring 1% Cu enzymes and measuring <0.1% Ni enzymes are compared and discussed. As a result, this study extends L-edge sum rule analysis to virtually any 3d metal complex and any dilute biological samples that contain 3d metals.« less

L-edge sum rule analysis on 3d transition metal sites: from d 10 to d 0 and towards application to extremely dilute metallo-enzymes

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

Wang, Hongxin; Friedrich, Stephan; Li, Lei

According to L-edge sum rules, the number of 3d vacancies at a transition metal site is directly proportional to the integrated intensity of the L-edge X-ray absorption spectrum (XAS) for the corresponding metal complex. In this study, the numbers of 3d holes are characterized quantitatively or semi-quantitatively for a series of manganese (Mn) and nickel (Ni) complexes, including the electron configurations 3d 10 → 3d 0. In addition, extremely dilute (<0.1% wt/wt) Ni enzymes were examined by two different approaches: (1) by using a high resolution superconducting tunnel junction X-ray detector to obtain XAS spectra with a very high signal-to-noisemore » ratio, especially in the non-variant edge jump region; and (2) by adding an inert tracer to the sample that provides a prominent spectral feature to replace the weak edge jump for intensity normalization. In this publication, we present for the first time: (1) L-edge sum rule analysis for a series of Mn and Ni complexes that include electron configurations from an open shell 3d0 to a closed shell 3d 10; (2) a systematic analysis on the uncertainties, especially on that from the edge jump, which was missing in all previous reports; (3) a clearly-resolved edge jump between pre-L 3 and post-L 2 regions from an extremely dilute sample; (4) an evaluation of an alternative normalization standard for L-edge sum rule analysis. XAS from two copper (Cu) proteins measured using a conventional semiconductor X-ray detector are also repeated as bridges between Ni complexes and dilute Ni enzymes. The differences between measuring 1% Cu enzymes and measuring <0.1% Ni enzymes are compared and discussed. As a result, this study extends L-edge sum rule analysis to virtually any 3d metal complex and any dilute biological samples that contain 3d metals.« less

Catalytic cartridge SO.sub.3 decomposer

DOEpatents

Galloway, Terry R.

1982-01-01

A catalytic cartridge surrounding a heat pipe driven by a heat source is utilized as a SO.sub.3 decomposer for thermochemical hydrogen production. The cartridge has two embodiments, a cross-flow cartridge and an axial flow cartridge. In the cross-flow cartridge, SO.sub.3 gas is flowed through a chamber and incident normally to a catalyst coated tube extending through the chamber, the catalyst coated tube surrounding the heat pipe. In the axial-flow cartridge, SO.sub.3 gas is flowed through the annular space between concentric inner and outer cylindrical walls, the inner cylindrical wall being coated by a catalyst and surrounding the heat pipe. The modular cartridge decomposer provides high thermal efficiency, high conversion efficiency, and increased safety.

Modeling Geometric Arrangements of TiO2-Based Catalyst Substrates and Isotropic Light Sources to Enhance the Efficiency of a Photocatalystic Oxidation (PCO) Reactor

NASA Technical Reports Server (NTRS)

Richards, Jeffrey T.; Levine, Lanfang H.; Husk, Geoffrey K.

2011-01-01

The closed confined environments of the ISS, as well as in future spacecraft for exploration beyond LEO, provide many challenges to crew health. One such challenge is the availability of a robust, energy efficient, and re-generable air revitalization system that controls trace volatile organic contaminants (VOCs) to levels below a specified spacecraft maximum allowable concentration (SMAC). Photocatalytic oxidation (PCO), which is capable of mineralizing VOCs at room temperature and of accommodating a high volumetric flow, is being evaluated as an alternative trace contaminant control technology. In an architecture of a combined air and water management system, placing a PCO unit before a condensing heat exchanger for humidity control will greatly reduce the organic load into the humidity condensate loop ofthe water processing assembly (WPA) thereby enhancing the life cycle economics ofthe WPA. This targeted application dictates a single pass efficiency of greater than 90% for polar VOCs. Although this target was met in laboratory bench-scaled reactors, no commercial or SBIR-developed prototype PCO units examined to date have achieved this goal. Furthermore, the formation of partial oxidation products (e.g., acetaldehyde) was not eliminated. It is known that single pass efficiency and partial oxidation are strongly dependent upon the contact time and catalyst illumination, hence the requirement for an efficient reactor design. The objective of this study is to maximize the apparent contact time and illuminated catalyst surface area at a given reactor volume and volumetric flow. In this study, a Ti02-based photocatalyst is assumed to be immobilized on porous substrate panels and illumination derived from linear isotropic light sources. Mathematical modeling using computational fluid dynamics (CFD) analyses were performed to investigate the effect of: 1) the geometry and configuration of catalyst-coated substrate panels, 2) porosity of the supporting substrate, and 3) varying the light source and spacing on contact time and illuminated catalyst area.

S-Duct Engine Inlet Flow Control Using SDBD Plasma Streamwise Vortex Generators

NASA Astrophysics Data System (ADS)

Kelley, Christopher; He, Chuan; Corke, Thomas

2009-11-01

The results of a numerical simulation and experiment characterizing the performance of plasma streamwise vortex generators in controlling separation and secondary flow within a serpentine, diffusing duct are presented. A no flow control case is first run to check agreement of location of separation, development of secondary flow, and total pressure recovery between the experiment and numerical results. Upon validation, passive vane-type vortex generators and plasma streamwise vortex generators are implemented to increase total pressure recovery and reduce flow distortion at the aerodynamic interface plane: the exit of the S-duct. Total pressure recovery is found experimentally with a pitot probe rake assembly at the aerodynamic interface plane. Stagnation pressure distortion descriptors are also presented to show the performance increase with plasma streamwise vortex generators in comparison to the baseline no flow control case. These performance parameters show that streamwise plasma vortex generators are an effective alternative to vane-type vortex generators in total pressure recovery and total pressure distortion reduction in S-duct inlets.

Development of the Monolith Froth Reactor for Catalytic Wet Oxidation of CELSS Model Wastes

NASA Technical Reports Server (NTRS)

Abraham, Martin; Fisher, John W.

1995-01-01

The aqueous phase oxidation of acetic acid, used as a model compound for the treatment of CELSS (Controlled Ecological Life Support System) waste, was carried out in the monolith froth reactor which utilizes two-phase flow in the monolith channels. The catalytic oxidation of acetic acid was carried out over a Pt/Al2O3 catalyst, prepared at The University of Tulsa, at temperatures and pressures below the critical point of water. The effect of externally controllable parameters (temperature, liquid flow rate, distributor plate orifice size, pitch, and catalyst distance from the distributor plate) on the rate of acetic acid oxidation was investigated. Results indicate reaction rate increased with increasing temperature and exhibited a maximum with respect to liquid flow rate. The apparent activation energy calculated from reaction rate data was 99.7 kJ/mol. This value is similar to values reported for the oxidation of acetic acid in other systems and is comparable to intrinsic values calculated for oxidation reactions. The kinetic data were modeled using simple power law kinetics. The effect of "froth" feed system characteristics was also investigated. Results indicate that the reaction rate exhibits a maximum with respect to distributor plate orifice size, pitch, and catalyst distance from the distributor plate. Fundamental results obtained were used to extrapolate where the complete removal of acetic acid would be obtained and for the design and operation of a full scale CELSS treatment system.

Application of Heterogeneous Copper Catalyst in a Continuous Flow Process: Dehydrogenation of Cyclohexanol

ERIC Educational Resources Information Center

Glin´ski, Marek; Ulkowska, Urszula; Iwanek, Ewa

2016-01-01

In this laboratory experiment, the synthesis of a supported solid catalyst (Cu/SiO2) and its application in the dehydrogenation of cyclohexanol performed under flow conditions was studied. The experiment was planned for a group of two or three students for two 6 h long sessions. The copper catalyst was synthesized using incipient wetness…

Enhancing Zeolite Performance by Catalyst Shaping in a Mesoscale Continuous-Flow Diels-Alder Process.

PubMed

Seghers, Sofie; Lefevere, Jasper; Mullens, Steven; De Vylder, Anton; Thybaut, Joris W; Stevens, Christian V

2018-03-26

In contrast to most lab-scale batch procedures, a continuous-flow implementation requires a thorough consideration of the solid catalyst design. In a previous study, irregular zeolite pellets were applied in a miniaturized continuous-flow reactor for the Diels-Alder reaction in the construction of norbornene scaffolds. After having faced the challenges of continuous operation, the aim of this study is to exploit catalyst structuring. To this end, microspheres with high uniformity and various sphere diameters were synthesized according to the vibrational droplet coagulation method. The influence of the use of these novel zeolite shapes in a mesoscale continuous-flow Diels-Alder process of cyclopentadiene and methyl acrylate is discussed. An impressive enhancement of catalyst lifetime is demonstrated, as even after a doubled process time of 14 h, the microspheres still exceeded the conversion after 7 h when using zeolite pellets by 30 %. A dual reason is found for this beneficial impact of catalyst shaping. The significant improvement in catalyst longevity can be attributed to the interplay of the chemical composition and the porosity structure of the microspheres. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalytic microwave pyrolysis of oil palm fiber (OPF) for the biochar production.

PubMed

Hossain, Md Arafat; Ganesan, Poo Balan; Sandaran, Shanti Chandran; Rozali, Shaifulazuar Bin; Krishnasamy, Sivakumar

2017-12-01

Microwave pyrolysis of oil palm fiber (OPF) with three types of Na-based catalysts was experimentally investigated to produce biochar. Sodium hydroxide (NaOH), sodium chloride (NaCl), and sodium carbonate (Na 2 CO 3 ) with purity 99.9% were selected for this investigation. Microwave muffle reactor (Model: HAMiab-C1500) with a microwave power controller including a microwave generator was used to perform the microwave pyrolysis. OPF particles were used after removing foreign materials, impurities, and dust. Microwave power ranges from 400 to 900 W, temperature ranges from 450 to 700 °C, and N 2 flow rates ranges from 200 to -1200 cm 3 /min were used along with all three Na-based catalysts for this investigation. Lower microwave power, temperature, and N 2 flow rate have been found favorable for higher yield of biochar. NaOH is to be found as the more suitable catalyst than NaCl and Na 2 CO 3 to produce biochar. A maximum biochar yield (51.42 wt%) has been found by using the catalysts NaOH at N 2 flow rate of 200 cm 3 /min. One sample of the biochar (maximum yield without catalysts) was selected for further characterization via thermo gravimetric analysis (TGA), scanning electron microscopy (SEM), BET surface area, Fourier transform infrared spectroscopy (FTIR), and ultimate and proximate analysis. SEM and BET surface area analysis showed the presence of some pores in the biochar. High percentage of carbon (60.24 wt%) was also recorded in the sample biochar. The pores and high percentage of carbon of biochar have significant impact on soil fertilization by increasing the carbon sequestration in the soil. It assists to slow down the decomposition rate of nutrients from soil and therefore enhances the soil quality.

Research on oxidation by air and tempering of Raney nickel electrocatalysts for the H2 anodes of alkali combustion materials cells. Thesis - Braunschweig Technische Univ., 1982

NASA Technical Reports Server (NTRS)

Selbach, H. J.

1984-01-01

The controlled oxidation in air of Raney nickel electrocatalysts was studied, with special attention paid to the quantitative analysis of nickel hydroxide. The content of the latter was determined through X-ray studies, thermogravimetric measurements, and spectral photometric examinations. The dependence of the content on the drying of activated catalyst is determined. The influence of nickel hydroxide on the electrochemical parameters of the catalyst, such as diffusion polarization, is studied, including a measurement of the exchange current density using the potential drop method. Conservation by oxidation in air with ancillary stabilization of the oxide in an H2 flow at 300 C is explored, including reduction by H2, the influence of tempering time, and structural studies on conserved and stabilized catalyst, long term research on the catalyst, including the influence of aging on the reduced catalyst, and the results of impedance measurements are presented.

Down-flow moving-bed gasifier with catalyst recycle

DOEpatents

Halow, John S.

1999-01-01

The gasification of coal and other carbonaceous materials by an endothermic gasification reaction is achieved in the presence of a catalyst in a down-flow, moving-bed gasifier. Catalyst is removed along with ash from the gasifier and is then sufficiently heated in a riser/burner by the combustion of residual carbon in the ash to volatilize the catalyst. This volatilized catalyst is returned to the gasifier where it uniformly contacts and condenses on the carbonaceous material. Also, the hot gaseous combustion products resulting from the combustion of the carbon in the ash along with excess air are introduced into the gasifier for providing heat energy used in the endothermic reaction.

Chemical forms of sulfur in geological and archeological asphaltenes from Middle East, France, and Spain determined by sulfur K- and L-edge X-ray absorption near-edge structure spectroscopy

NASA Astrophysics Data System (ADS)

Sarret, Géraldine; Connan, Jacques; Kasrai, Masoud; Bancroft, G. Michael; Charrié-Duhaut, Armelle; Lemoine, Sylvie; Adam, Pierre; Albrecht, Pierre; Eybert-Bérard, Laurent

1999-11-01

Asphaltene samples extracted from archeological and geological bitumens from the Middle East, France, and Spain were studied by sulfur K- and L-edge X-ray absorption near-edge structure (XANES) spectroscopy in combination with isotopic analyses (δ 13C and δD). Within each series, the samples were genetically related by their δ 13C values. The gross and elemental composition and the δD values were used to characterize the weathering state of the samples. Sulfur K- and L-edge XANES results show that in all the samples, dibenzothiophenes are the dominant forms of sulfur. In the least oxidized asphaltenes, minor species include disulfides, alkyl and aryl sulfides, and sulfoxides. With increasing alteration the proportion of oxidized sulfur (sulfoxides, sulfones, sulfonates and sulfates) increases, whereas the disulfide and sulfide content decreases. This evolution is observed in all the series, regardless of the origin of the asphaltenes. This work illustrates the advantages of XANES spectroscopy as a selective probe for determining sulfur speciation in natural samples. It also shows that S K- and L-edge XANES spectroscopy are complementary for identifying the oxidized and reduced forms of sulfur, respectively.

Defects and Interfaces on PtPb Nanoplates Boost Fuel Cell Electrocatalysis.

PubMed

Sun, Yingjun; Liang, Yanxia; Luo, Mingchuan; Lv, Fan; Qin, Yingnan; Wang, Lei; Xu, Chuan; Fu, Engang; Guo, Shaojun

2018-01-01

Nanostructured Pt is the most efficient single-metal catalyst for fuel cell technology. Great efforts have been devoted to optimizing the Pt-based alloy nanocrystals with desired structure, composition, and shape for boosting the electrocatalytic activity. However, these well-known controls still show the limited ability in maximizing the Pt utilization efficiency for achieving more efficient fuel cell catalysis. Herein, a new strategy for maximizing the fuel cell catalysis by controlling/tuning the defects and interfaces of PtPb nanoplates using ion irradiation technique is reported. The defects and interfaces on PtPb nanoplates, controlled by the fluence of incident C + ions, make them exhibit the volcano-like electrocatalytic activity for methanol oxidation reaction (MOR), ethanol oxidation reaction (EOR), and oxygen reduction reaction (ORR) as a function of ion irradiation fluence. The optimized PtPb nanoplates with the mixed structure of dislocations, subgrain boundaries, and small amorphous domains are the most active for MOR, EOR, and ORR. They can also maintain high catalytic stability in acid solution. This work highlights the impact and significance of inducing/controlling the defects and interfaces on Pt-based nanocrystals toward maximizing the catalytic performance by advanced ion irradiation strategy. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalytic cartridge SO/sub 3/ decomposer

DOEpatents

Galloway, T.R.

1980-11-18

A catalytic cartridge surrounding a heat pipe driven by a heat source is utilized as a SO/sub 3/ decomposer for thermochemical hydrogen production. The cartridge has two embodiments, a cross-flow cartridge and an axial flow cartridge. In the cross-flow cartridge, SO/sub 3/ gas is flowed through a chamber and incident normally to a catalyst coated tube extending through the chamber, the catalyst coated tube surrounding the heat pipe. In the axial-flow cartridge, SO/sub 3/ gas is flowed through the annular space between concentric inner and outer cylindrical walls, the inner cylindrical wall being coated by a catalyst and surrounding the heat pipe. The modular cartridge decomposer provides high thermal efficiency, high conversion efficiency, and increased safety. A fusion reactor may be used as the heat source.

Diesel particulate abatement via wall-flow traps based on perovskite catalysts.

PubMed

Fino, Debora; Russo, Nunzio; Saracco, Guido; Specchia, Vito

2003-01-01

It is probably redundant to stress how extensive are nowadays the attempts to reduce the diesel particulate emissions from automotive and stationary sources. The present paper looks into a technology relied on a catalytic trap based on a SiC wall-flow monolith lined with suitable catalysts for the sake of promoting a more complete and faster regeneration after particulate capture. All the major steps of the catalytic filter preparation are dealt with, including: the synthesis and choice of the proper catalyst and trap materials, the development of an in situ catalyst deposition technique, the bench testing of the derived catalytic wall-flow. The best catalyst selected was the perovskite La0.9K0.1Cr0.9O3-delta. The filtration efficiency and the pressure drop of the catalytic and non-catalytic monoliths were evaluated on a diesel engine bench under various operating conditions.

Ionic Liquid Droplet Microreactor for Catalysis Reactions Not at Equilibrium.

PubMed

Zhang, Ming; Ettelaie, Rammile; Yan, Tao; Zhang, Suojiang; Cheng, Fangqin; Binks, Bernard P; Yang, Hengquan

2017-12-06

We develop a novel strategy to more effectively and controllably process continuous enzymatic or homogeneous catalysis reactions based on nonaqueous Pickering emulsions. A key element of this strategy is "bottom-up" construction of a macroscale continuous flow reaction system through packing catalyst-containing micron-sized ionic liquid (IL) droplet in oil in a column reactor. Due to the continuous influx of reactants into the droplet microreactors and the continuous release of products from the droplet microreactors, catalysis reactions in such a system can take place without limitations arising from establishment of the reaction equilibrium and catalyst separation, inherent in conventional batch reactions. As proof of the concept, enzymatic enantioselective trans-esterification and CuI-catalyzed cycloaddition reactions using this IL droplet-based flow system both exhibit 8 to 25-fold enhancement in catalysis efficiency compared to their batch counterparts, and a durability of at least 4000 h for the enantioselective trans-esterification of 1-phenylethyl alcohol, otherwise unattainable in their batch counterparts. We further establish a theoretical model for such a catalysis system working under nonequilibrium conditions, which not only supports the experimental results but also helps to predict reaction progress at a microscale level. Being operationally simple, efficient, and adaptive, this strategy provides an unprecedented platform for practical applications of enzymes and homogeneous catalysts even at a controllable level.

The Sugar Model: Catalytic Flow Reactor Dynamics of Pyruvaldehyde Synthesis from Triose Catalyzed by Poly-L-Lysine Contained in a Dialyzer

NASA Technical Reports Server (NTRS)

Weber, Arthur L.; DeVincenzi, Donald (Technical Monitor)

2000-01-01

The formation of pyruvaldehyde from triose sugars was catalyzed by poly-L-lysine contained in a small dialyzer (100 MWCO) suspended in a much larger triose substrate reservoir. The polylysine confined in the dialyzer functioned as a catalytic flow reactor that constantly brought in triose from the substrate reservoir by diffusion to offset the drop in triose concentration within the reactor caused by its conversion to pyruvaldehyde. A 400 mM solution of poly-L-lysine contained in a 0.35 ml dialyzer placed in a 120 ml solution of triose substrate (pH 5.5, 40 C) generated pyruvaldehyde 11 -times faster than an a control reaction without the catalytic dialyzer. However, since the catalytic dialyzer's volume was 343-times smaller than the control reaction, the synthetic intensity (rate/volume) of pyruvaldehyde synthesis within the catalytic dialyzer was 3400-times greater than that of the control reaction and substrate solution. A similar result was obtained using a dialyzer with a 500 MWCO value. Acting as a catalytic flow reactor the polylysine catalytic dialyzer synthesized about 3.5 molecules of pyruvaldehyde per lysine residue in 7 days -- an amount of triose equal to twice the weight of the catalyst. At 7 days the catalytic activity of polylysine was 16% of its initial value, a result indicating catalyst-poisoning caused by reaction of pyruvaldehyde with the e-amino groups of polylysine. The dialyzer method of catalyst containment was selected it provides a simple, flexible, and easily manipulated experimental system for studying the dynamics and evolutionary development of confined autocatalytic processes related to the origin of life under anaerobic conditions.

Six-flow operations for catalyst development in Fischer-Tropsch synthesis: Bridging the gap between high-throughput experimentation and extensive product evaluation

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

Sartipi, Sina, E-mail: S.Sartipi@tudelft.nl, E-mail: J.Gascon@tudelft.nl; Jansma, Harrie; Bosma, Duco

2013-12-15

Design and operation of a “six-flow fixed-bed microreactor” setup for Fischer-Tropsch synthesis (FTS) is described. The unit consists of feed and mixing, flow division, reaction, separation, and analysis sections. The reactor system is made of five heating blocks with individual temperature controllers, assuring an identical isothermal zone of at least 10 cm along six fixed-bed microreactor inserts (4 mm inner diameter). Such a lab-scale setup allows running six experiments in parallel, under equal feed composition, reaction temperature, and conditions of separation and analysis equipment. It permits separate collection of wax and liquid samples (from each flow line), allowing operation with highmore » productivities of C5+ hydrocarbons. The latter is crucial for a complete understanding of FTS product compositions and will represent an advantage over high-throughput setups with more than ten flows where such instrumental considerations lead to elevated equipment volume, cost, and operation complexity. The identical performance (of the six flows) under similar reaction conditions was assured by testing a same catalyst batch, loaded in all microreactors.« less

Catalyst Residence Time Distributions in Riser Reactors for Catalytic Fast Pyrolysis. Part 2: Pilot-Scale Simulations and Operational Parameter Study

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

Foust, Thomas D.; Ziegler, Jack L.; Pannala, Sreekanth

2017-02-21

Here, wsing the validated simulation model developed in part one of this study for biomass catalytic fast pyrolysis (CFP), we assess the functional utility of using this validated model to assist in the development of CFP processes in fluidized catalytic cracking (FCC) reactors to a commercially viable state. Specifically, we examine the effects of mass flow rates, boundary conditions (BCs), pyrolysis vapor molecular weight variation, and the impact of the chemical cracking kinetics on the catalyst residence times. The factors that had the largest impact on the catalyst residence time included the feed stock molecular weight and the degree ofmore » chemical cracking as controlled by the catalyst activity. Lastly, because FCC reactors have primarily been developed and utilized for petroleum cracking, we perform a comparison analysis of CFP with petroleum and show the operating regimes are fundamentally different.« less

Toward Small-Diameter Carbon Nanotubes Synthesized from Captured Carbon Dioxide: Critical Role of Catalyst Coarsening.

PubMed

Douglas, Anna; Carter, Rachel; Li, Mengya; Pint, Cary L

2018-06-06

Small-diameter carbon nanotubes (CNTs) often require increased sophistication and control in synthesis processes, but exhibit improved physical properties and greater economic value over their larger-diameter counterparts. Here, we study mechanisms controlling the electrochemical synthesis of CNTs from the capture and conversion of ambient CO 2 in molten salts and leverage this understanding to achieve the smallest-diameter CNTs ever reported in the literature from sustainable electrochemical synthesis routes, including some few-walled CNTs. Here, Fe catalyst layers are deposited at different thicknesses onto stainless steel to produce cathodes, and atomic layer deposition of Al 2 O 3 is performed on Ni to produce a corrosion-resistant anode. Our findings indicate a correlation between the CNT diameter and Fe metal layer thickness following electrochemical catalyst reduction at the cathode-molten salt interface. Further, catalyst coarsening during long duration synthesis experiments leads to a 2× increase in average diameters from 3 to 60 min durations, with CNTs produced after 3 min exhibiting a tight diameter distribution centered near ∼10 nm. Energy consumption analysis for the conversion of CO 2 into CNTs demonstrates energy input costs much lower than the value of CNTs-a concept that strictly requires and motivates small-diameter CNTs-and is more favorable compared to other costly CO 2 conversion techniques that produce lower-value materials and products.

Forecasting the zeolite-containing catalyst activity in catalytic cracking technology taking into account the feedstock composition

NASA Astrophysics Data System (ADS)

Ivashkina, Elena; Nazarova, Galina; Shafran, Tatyana; Stebeneva, Valeriya

2017-08-01

The effect of the feedstock composition and the process conditions on the current catalyst activity in catalytic cracking technology using a mathematical model is performed in this research. The mathematical model takes into account the catalyst deactivation by coke for primary and secondary cracking reactions. The investigation results have shown that the feedstock has significant effect on the yield and the content of coke on the catalyst. Thus, the relative catalyst activity is significantly reduced by 7.5-10.7 %. With increasing the catalytic cracking temperature due to the catalyst flow temperature rising, the coke content and the yield per feedstock increase and the catalyst activity decreases by 5.3-7.7%. Rising the process temperature together with the catalyst circulation ratio contributes to increase of the coke yield per feedstock in the catalytic cracking and decrease of the coke content on the catalyst. It is connected with the catalyst flow rising to the riser and the contact time decreasing in the reaction zone. Also, the catalyst activity decreases in the range of 3.8-5.5% relatively to the regenerated catalyst activity (83 %).

Surface-subsurface turbulent interaction at the interface of a permeable bed: influence of the wall permeability

NASA Astrophysics Data System (ADS)

Kim, T.; Blois, G.; Best, J.; Christensen, K. T.

2017-12-01

Coarse-gravel river beds possess a high degree of permeability. Flow interactions between surface and subsurface flow across the bed interface is key to a number of natural processes occurring in the hyporheic zone. In fact, it is increasingly recognized that these interactions drive mass, momentum and energy transport across the interface, and consequently control biochemical processes as well as stability of sediments. The current study explores the role of the wall permeability in surface and subsurface flow interaction under controlled experimental conditions on a physical model of a gravel bed. The present wall model was constructed by five layers of cubically arranged spheres (d=25.4mm, where d is a diameter) providing 48% of porosity. Surface topography was removed by cutting half of a diameter on the top layer of spheres to render the flow surface smooth and highlight the impact of the permeability on the overlying flow. An impermeable smooth wall was also considered as a baseline of comparison for the permeable wall flow. To obtain basic flow statistics, low-frame-rate high-resolution PIV measurements were performed first in the streamwise-wall-normal (x-y) plane and refractive-index matching was employed to optically access the flow within the permeable wall. Time-resolved PIV experiments in the same facility were followed to investigate the flow interaction across the wall interface in sptaio-temporal domain. In this paper, a detailed analysis of the first and second order velocity statistics as well as the amplitude modulation for the flow overlying the permeable smooth wall will be presented.

Catalytic nanoporous membranes

DOEpatents

Pellin, Michael J [Naperville, IL; Hryn, John N [Naperville, IL; Elam, Jeffrey W [Elmhurst, IL

2009-12-01

A nanoporous catalytic membrane which displays several unique features including pores which can go through the entire thickness of the membrane. The membrane has a higher catalytic and product selectivity than conventional catalysts. Anodic aluminum oxide (AAO) membranes serve as the catalyst substrate. This substrate is then subjected to Atomic Layer Deposition (ALD), which allows the controlled narrowing of the pores from 40 nm to 10 nm in the substrate by deposition of a preparatory material. Subsequent deposition of a catalytic layer on the inner surfaces of the pores reduces pore sizes to less than 10 nm and allows for a higher degree of reaction selectivity. The small pore sizes allow control over which molecules enter the pores, and the flow-through feature can allow for partial oxidation of reactant species as opposed to complete oxidation. A nanoporous separation membrane, produced by ALD is also provided for use in gaseous and liquid separations. The membrane has a high flow rate of material with 100% selectivity.

Amorphous nickel boride membrane on a platinum-nickel alloy surface for enhanced oxygen reduction reaction.

PubMed

He, Daping; Zhang, Libo; He, Dongsheng; Zhou, Gang; Lin, Yue; Deng, Zhaoxiang; Hong, Xun; Wu, Yuen; Chen, Chen; Li, Yadong

2016-08-09

The low activity of the oxygen reduction reaction in polymer electrolyte membrane fuel cells is a major barrier for electrocatalysis, and hence needs to be optimized. Tuning the surface electronic structure of platinum-based bimetallic alloys, a promising oxygen reduction reaction catalyst, plays a key role in controlling its interaction with reactants, and thus affects the efficiency. Here we report that a dealloying process can be utilized to experimentally fabricate the interface between dealloyed platinum-nickel alloy and amorphous nickel boride membrane. The coating membrane works as an electron acceptor to tune the surface electronic structure of the platinum-nickel catalyst, and this composite catalyst composed of crystalline platinum-nickel covered by amorphous nickel boride achieves a 27-times enhancement in mass activity relative to commercial platinum/carbon at 0.9 V for the oxygen reduction reaction performance. Moreover, this interactional effect between a crystalline surface and amorphous membrane can be readily generalized to facilitate the 3-times higher catalytic activity of commercial platinum/carbon.

Experimental analysis of the flow near the boundary of random porous media

NASA Astrophysics Data System (ADS)

Wu, Zhenxing; Mirbod, Parisa

2018-04-01

The aim of this work is to experimentally examine flow over and near random porous media. Different porous materials were chosen to achieve porosity ranging from 0.95 to 0.99. In this study, we report the detailed velocity measurements of the flow over and near random porous material inside a rectangular duct using a planar particle image velocimetry (PIV) technique. By controlling the flow rate, two different Reynolds numbers were achieved. We determined the slip velocity at the interface between the porous media and free flow. Values of the slip velocity normalized either by the maximum flow velocity or by the shear rate at the interface and the screening distance K1/2 were found to depend on porosity. It was also shown that the depth of penetration inside the porous material was larger than the screening length using Brinkman's prediction. Moreover, we examined a model for the laminar coupled flow over and inside porous media and analyzed the permeability of a random porous medium. This study provided detailed analysis of flow over and at the interface of various specific random porous media using the PIV technique. This analysis has the potential to serve as a first step toward using random porous media as a new passive technique to control the flow over smooth surfaces.

4d Electronic structure analysis of ruthenium in the perovskite oxides by Ru K- and L-edge XAS.

PubMed

Kim, J Y; Hwang, S H; Kim, S J; Demazeau, G; Choy, J H; Shimada, H

2001-03-01

The 4d electronic structure of ruthenium in the perovskite oxides, La2MRuIVO6 (M = Zn, Mg, and Li) and Ba2YRuVO6, has been investigated by the Ru K-and L-edge XANES and EXAFS analyses. Such X-ray absorption spectroscopic results clarify that the RuIV (d4) and RuV (d3) ions are stabilized in nearly regular Oh site. Comparing the Ru L-edge XANES spectra of perovskites containing isovalent ruthenium, it has been found that the t2g state is mainly influenced by A site cation, whereas the eg is mainly affected by neighboring B site cation. The experimental EXAFS spectra in the range of R < or = approximately 4.5 A are well reproduced by ab-initio calculation based on crystallographic data, which supports the long-range structure presented by Rietveld refinement.

Structural dynamic and thermal stress analysis of nuclear reactor vessel support system

NASA Technical Reports Server (NTRS)

Chi-Diango, J.

1972-01-01

A nuclear reactor vessel is supported by a Z-ring and a box ring girder. The two proposed structural configurations to transmit the loads from the Z-ring and the box ring girder to the foundation are shown. The cantilever concrete ledge transmitting the load from the Z-ring and the box girder via the cavity wall to the foundation is shown, along with the loads being transmitted through one of the six steel columns. Both of these two supporting systems were analyzed by using rigid format 9 of NASTRAN for dynamic loads, and the thermal stresses were analyzed by AXISOL. The six column configuration was modeled by a combination of plate and bar elements, and the concrete cantilever ledge configuration was modeled by plate elements. Both configurations were found structurally satisfactory; however, nonstructural considerations favored the concrete cantilever ledge.

Down-flow moving-bed gasifier with catalyst recycle

DOEpatents

Halow, J.S.

1999-04-20

The gasification of coal and other carbonaceous materials by an endothermic gasification reaction is achieved in the presence of a catalyst in a down-flow, moving-bed gasifier. Catalyst is removed along with ash from the gasifier and is then sufficiently heated in a riser/burner by the combustion of residual carbon in the ash to volatilize the catalyst. This volatilized catalyst is returned to the gasifier where it uniformly contacts and condenses on the carbonaceous material. Also, the hot gaseous combustion products resulting from the combustion of the carbon in the ash along with excess air are introduced into the gasifier for providing heat energy used in the endothermic reaction. 1 fig.

Catalyst and process development for synthesis gas conversion to isobutylene. Quarterly report, October 1, 1992--December 31, 1992

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

Anthony, R.G.; Akgerman, A.

1993-02-01

The objectives of this project are to develop a new catalyst, the kinetics for this catalyst, reactor models for trickle bed, slurry and fixed bed reactors, and simulate the performance of fixed bed trickle flow reactors, slurry flow reactors, and fixed bed gas phase reactors for conversion of a hydrogen lean synthesis gas to isobutylene. The goals for the quarter include: (1) Conduct experiments using a trickle bed reactor to determine the effect of reactor type on the product distribution. (2) Use spherical pellets of silica as a support for zirconia for the purpose of increasing surface, area and performancemore » of the catalysts. (3) Conduct exploratory experiments to determine the effect of super critical drying of the catalyst on the catalyst surface area and performance. (4) Prepare a ceria/zirconia catalyst by the precipitation method.« less

Redox chemistry at liquid/liquid interfaces

NASA Technical Reports Server (NTRS)

Volkov, A. G.; Deamer, D. W.

1997-01-01

The interface between two immiscible liquids with immobilized photosynthetic pigments can serve as the simplest model of a biological membrane convenient for the investigation of photoprocesses accompanied by spatial separation of charges. As it follows from thermodynamics, if the resolvation energies of substrates and products are very different, the interface between two immiscible liquids may act as a catalyst. Theoretical aspects of charge transfer reactions at oil/water interfaces are discussed. Conditions under which the free energy of activation of the interfacial reaction of electron transfer decreases are established. The activation energy of electron transfer depends on the charges of the reactants and dielectric permittivity of the non-aqueous phase. This can be useful when choosing a pair of immiscible solvents to decrease the activation energy of the reaction in question or to inhibit an undesired process. Experimental interfacial catalytic systems are discussed. Amphiphilic molecules such as chlorophyll or porphyrins were studied as catalysts of electron transfer reactions at the oil/water interface.

Optimal Power Flow Pursuit

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

Dall'Anese, Emiliano; Simonetto, Andrea

This paper considers distribution networks featuring inverter-interfaced distributed energy resources, and develops distributed feedback controllers that continuously drive the inverter output powers to solutions of AC optimal power flow (OPF) problems. Particularly, the controllers update the power setpoints based on voltage measurements as well as given (time-varying) OPF targets, and entail elementary operations implementable onto low-cost microcontrollers that accompany power-electronics interfaces of gateways and inverters. The design of the control framework is based on suitable linear approximations of the AC power-flow equations as well as Lagrangian regularization methods. Convergence and OPF-target tracking capabilities of the controllers are analytically established. Overall,more » the proposed method allows to bypass traditional hierarchical setups where feedback control and optimization operate at distinct time scales, and to enable real-time optimization of distribution systems.« less

Visible-light photochemical activity of heterostructured core-shell materials composed of selected ternary titanates and ferrites coated by tiO2.

PubMed

Li, Li; Liu, Xuan; Zhang, Yiling; Nuhfer, Noel T; Barmak, Katayun; Salvador, Paul A; Rohrer, Gregory S

2013-06-12

Heterostructured photocatalysts comprised of microcrystalline (mc-) cores and nanostructured (ns-) shells were prepared by the sol-gel method. The ability of titania-coated ATiO3 (A = Fe, Pb) and AFeO3 (A = Bi, La, Y) catalysts to degrade methylene blue in visible light (λ > 420 nm) was compared. The catalysts with the titanate cores had enhanced photocatalytic activities for methylene blue degradation compared to their components alone, whereas the catalysts with ferrite cores did not. The temperature at which the ns-titania shell is crystallized influences the photocatalytic dye degradation. mc-FeTiO3/ns-TiO2 annealed at 500 °C shows the highest reaction rate. Fe-doped TiO2, which absorbs visible light, did not show enhanced photocatalytic activity for methylene blue degradation. This result indicates that iron contamination is not a decisive factor in the reduced reactivity of the titania coated ferrite catalysts. The higher reactivity of materials with the titanate cores suggests that photogenerated charge carriers are more easily transported across the titanate-titanate interface than the ferrite-titanate interface and this provides guidance for materials selection in composite catalyst design.

Metrology for Fuel Cell Manufacturing

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

Stocker, Michael; Stanfield, Eric

2015-02-04

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

Investigating the Catalytic Growth of Carbon Nanotubes with In Situ Raman Monitoring

DTIC Science & Technology

2015-06-01

single-walled carbon nanotube growth using cobalt deposited on Si/SiO2 as a model system. In situ Raman studies revealed that thin catalyst layers... cobalt thickness were studied. Surface analyses showed that during the catalyst preparation, catalyst atoms at the interface with silica form small...nanostructures. However, highly-reducing conditions are required to reduce the small silicate domains into small cobalt particles able to grow single-walled

Direct observation of morphological evolution of a catalyst during carbon nanotube forest growth: new insights into growth and growth termination

NASA Astrophysics Data System (ADS)

Jeong, Seojeong; Lee, Jaegeun; Kim, Hwan-Chul; Hwang, Jun Yeon; Ku, Bon-Cheol; Zakharov, Dmitri N.; Maruyama, Benji; Stach, Eric A.; Kim, Seung Min

2016-01-01

In this study, we develop a new methodology for transmission electron microscopy (TEM) analysis that enables us to directly investigate the interface between carbon nanotube (CNT) arrays and the catalyst and support layers for CNT forest growth without any damage induced by a post-growth TEM sample preparation. Using this methodology, we perform in situ and ex situ TEM investigations on the evolution of the morphology of the catalyst particles and observe the catalyst particles to climb up through CNT arrays during CNT forest growth. We speculate that the lifted catalysts significantly affect the growth and growth termination of CNT forests along with Ostwald ripening and sub-surface diffusion. Thus, we propose a modified growth termination model which better explains various phenomena related to the growth and growth termination of CNT forests.In this study, we develop a new methodology for transmission electron microscopy (TEM) analysis that enables us to directly investigate the interface between carbon nanotube (CNT) arrays and the catalyst and support layers for CNT forest growth without any damage induced by a post-growth TEM sample preparation. Using this methodology, we perform in situ and ex situ TEM investigations on the evolution of the morphology of the catalyst particles and observe the catalyst particles to climb up through CNT arrays during CNT forest growth. We speculate that the lifted catalysts significantly affect the growth and growth termination of CNT forests along with Ostwald ripening and sub-surface diffusion. Thus, we propose a modified growth termination model which better explains various phenomena related to the growth and growth termination of CNT forests. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr05547d

Catalyst Interface Engineering for Improved 2D Film Lift-Off and Transfer

PubMed Central

2016-01-01

The mechanisms by which chemical vapor deposited (CVD) graphene and hexagonal boron nitride (h-BN) films can be released from a growth catalyst, such as widely used copper (Cu) foil, are systematically explored as a basis for an improved lift-off transfer. We show how intercalation processes allow the local Cu oxidation at the interface followed by selective oxide dissolution, which gently releases the 2D material (2DM) film. Interfacial composition change and selective dissolution can thereby be achieved in a single step or split into two individual process steps. We demonstrate that this method is not only highly versatile but also yields graphene and h-BN films of high quality regarding surface contamination, layer coherence, defects, and electronic properties, without requiring additional post-transfer annealing. We highlight how such transfers rely on targeted corrosion at the catalyst interface and discuss this in context of the wider CVD growth and 2DM transfer literature, thereby fostering an improved general understanding of widely used transfer processes, which is essential to numerous other applications. PMID:27934130

Persistent differences between coastal and offshore kelp forest communities in a warming Gulf of Maine

PubMed Central

Lamb, Robert W.

2018-01-01

Kelp forests provide important ecosystem services, yet coastal kelp communities are increasingly altered by anthropogenic impacts. Kelp forests in remote, offshore locations may provide an informative contrast due to reduced impacts from local stressors. We tested the hypothesis that shallow kelp assemblages (12–15 m depth) and associated fish and benthic communities in the coastal southwest Gulf of Maine (GOM) differed significantly from sites on Cashes Ledge, 145 km offshore by sampling five coastal and three offshore sites at 43.0 +/- 0.07° N latitude. Offshore sites on Cashes Ledge supported the greatest density (47.8 plants m2) and standing crop biomass (5.5 kg m2 fresh weight) of the foundation species Saccharina latissima kelp at this depth in the Western North Atlantic. Offshore densities of S. latissima were over 150 times greater than at coastal sites, with similar but lower magnitude trends for congeneric S. digitata. Despite these differences, S. latissima underwent a significant 36.2% decrease between 1987 and 2015 on Cashes Ledge, concurrent with a rapid warming of the GOM and invasion by the kelp-encrusting bryozoan Membranipora membranacea. In contrast to kelp, the invasive red alga Dasysiphonia japonica was significantly more abundant at coastal sites, suggesting light or dispersal limitation offshore. Spatial differences in fish abundance mirrored those of kelp, as the average biomass of all fish on Cashes Ledge was 305 times greater than at the coastal sites. Remote video censuses of cod (Gadus morhua), cunner (Tautaogolabrus adspersus), and pollock (Pollachius virens) corroborated these findings. Understory benthic communities also differed between regions, with greater abundance of sessile invertebrates offshore. Populations of kelp-consuming sea urchins Stronglyocentrotus droebachiensis, were virtually absent from Cashes Ledge while small urchins were abundant onshore, suggesting recruitment limitation offshore. Despite widespread warming of the GOM since 1987, extraordinary spatial differences in the abundance of primary producers (kelp), consumers (cod) and benthic communities between coastal and offshore sites have persisted. The shallow kelp forest communities offshore on Cashes Ledge represent an oasis of unusually high kelp and fish abundance in the region, and as such, comprise a persistent abundance hotspot that is functionally significant for sustained biological productivity of offshore regions of the Gulf of Maine. PMID:29298307

X-ray Absorption Spectroscopy Systematics at the Tungsten L-Edge

PubMed Central

2015-01-01

A series of mononuclear six-coordinate tungsten compounds spanning formal oxidation states from 0 to +VI, largely in a ligand environment of inert chloride and/or phosphine, was interrogated by tungsten L-edge X-ray absorption spectroscopy. The L-edge spectra of this compound set, comprised of [W0(PMe3)6], [WIICl2(PMePh2)4], [WIIICl2(dppe)2][PF6] (dppe = 1,2-bis(diphenylphosphino)ethane), [WIVCl4(PMePh2)2], [WV(NPh)Cl3(PMe3)2], and [WVICl6], correlate with formal oxidation state and have usefulness as references for the interpretation of the L-edge spectra of tungsten compounds with redox-active ligands and ambiguous electronic structure descriptions. The utility of these spectra arises from the combined correlation of the estimated branching ratio of the L3,2-edges and the L1 rising-edge energy with metal Zeff, thereby permitting an assessment of effective metal oxidation state. An application of these reference spectra is illustrated by their use as backdrop for the L-edge X-ray absorption spectra of [WIV(mdt)2(CO)2] and [WIV(mdt)2(CN)2]2– (mdt2– = 1,2-dimethylethene-1,2-dithiolate), which shows that both compounds are effectively WIV species even though the mdt ligands exist at different redox levels in the two compounds. Use of metal L-edge XAS to assess a compound of uncertain formulation requires: (1) Placement of that data within the context of spectra offered by unambiguous calibrant compounds, preferably with the same coordination number and similar metal ligand distances. Such spectra assist in defining upper and/or lower limits for metal Zeff in the species of interest. (2) Evaluation of that data in conjunction with information from other physical methods, especially ligand K-edge XAS. (3) Increased care in interpretation if strong π-acceptor ligands, particularly CO, or π-donor ligands are present. The electron-withdrawing/donating nature of these ligand types, combined with relatively short metal–ligand distances, exaggerate the difference between formal oxidation state and metal Zeff or, as in the case of [WIV(mdt)2(CO)2], exert the subtle effect of modulating the redox level of other ligands in the coordination sphere. PMID:25068843

X-ray absorption spectroscopy systematics at the tungsten L-edge.

PubMed

Jayarathne, Upul; Chandrasekaran, Perumalreddy; Greene, Angelique F; Mague, Joel T; DeBeer, Serena; Lancaster, Kyle M; Sproules, Stephen; Donahue, James P

2014-08-18

A series of mononuclear six-coordinate tungsten compounds spanning formal oxidation states from 0 to +VI, largely in a ligand environment of inert chloride and/or phosphine, was interrogated by tungsten L-edge X-ray absorption spectroscopy. The L-edge spectra of this compound set, comprised of [W(0)(PMe3)6], [W(II)Cl2(PMePh2)4], [W(III)Cl2(dppe)2][PF6] (dppe = 1,2-bis(diphenylphosphino)ethane), [W(IV)Cl4(PMePh2)2], [W(V)(NPh)Cl3(PMe3)2], and [W(VI)Cl6], correlate with formal oxidation state and have usefulness as references for the interpretation of the L-edge spectra of tungsten compounds with redox-active ligands and ambiguous electronic structure descriptions. The utility of these spectra arises from the combined correlation of the estimated branching ratio of the L3,2-edges and the L1 rising-edge energy with metal Zeff, thereby permitting an assessment of effective metal oxidation state. An application of these reference spectra is illustrated by their use as backdrop for the L-edge X-ray absorption spectra of [W(IV)(mdt)2(CO)2] and [W(IV)(mdt)2(CN)2](2-) (mdt(2-) = 1,2-dimethylethene-1,2-dithiolate), which shows that both compounds are effectively W(IV) species even though the mdt ligands exist at different redox levels in the two compounds. Use of metal L-edge XAS to assess a compound of uncertain formulation requires: (1) Placement of that data within the context of spectra offered by unambiguous calibrant compounds, preferably with the same coordination number and similar metal ligand distances. Such spectra assist in defining upper and/or lower limits for metal Zeff in the species of interest. (2) Evaluation of that data in conjunction with information from other physical methods, especially ligand K-edge XAS. (3) Increased care in interpretation if strong π-acceptor ligands, particularly CO, or π-donor ligands are present. The electron-withdrawing/donating nature of these ligand types, combined with relatively short metal-ligand distances, exaggerate the difference between formal oxidation state and metal Zeff or, as in the case of [W(IV)(mdt)2(CO)2], exert the subtle effect of modulating the redox level of other ligands in the coordination sphere.

Persistent differences between coastal and offshore kelp forest communities in a warming Gulf of Maine.

PubMed

Witman, Jon D; Lamb, Robert W

2018-01-01

Kelp forests provide important ecosystem services, yet coastal kelp communities are increasingly altered by anthropogenic impacts. Kelp forests in remote, offshore locations may provide an informative contrast due to reduced impacts from local stressors. We tested the hypothesis that shallow kelp assemblages (12-15 m depth) and associated fish and benthic communities in the coastal southwest Gulf of Maine (GOM) differed significantly from sites on Cashes Ledge, 145 km offshore by sampling five coastal and three offshore sites at 43.0 +/- 0.07° N latitude. Offshore sites on Cashes Ledge supported the greatest density (47.8 plants m2) and standing crop biomass (5.5 kg m2 fresh weight) of the foundation species Saccharina latissima kelp at this depth in the Western North Atlantic. Offshore densities of S. latissima were over 150 times greater than at coastal sites, with similar but lower magnitude trends for congeneric S. digitata. Despite these differences, S. latissima underwent a significant 36.2% decrease between 1987 and 2015 on Cashes Ledge, concurrent with a rapid warming of the GOM and invasion by the kelp-encrusting bryozoan Membranipora membranacea. In contrast to kelp, the invasive red alga Dasysiphonia japonica was significantly more abundant at coastal sites, suggesting light or dispersal limitation offshore. Spatial differences in fish abundance mirrored those of kelp, as the average biomass of all fish on Cashes Ledge was 305 times greater than at the coastal sites. Remote video censuses of cod (Gadus morhua), cunner (Tautaogolabrus adspersus), and pollock (Pollachius virens) corroborated these findings. Understory benthic communities also differed between regions, with greater abundance of sessile invertebrates offshore. Populations of kelp-consuming sea urchins Stronglyocentrotus droebachiensis, were virtually absent from Cashes Ledge while small urchins were abundant onshore, suggesting recruitment limitation offshore. Despite widespread warming of the GOM since 1987, extraordinary spatial differences in the abundance of primary producers (kelp), consumers (cod) and benthic communities between coastal and offshore sites have persisted. The shallow kelp forest communities offshore on Cashes Ledge represent an oasis of unusually high kelp and fish abundance in the region, and as such, comprise a persistent abundance hotspot that is functionally significant for sustained biological productivity of offshore regions of the Gulf of Maine.

Hydrogenation of CO 2 on ZnO/Cu(100) and ZnO/Cu(111) Catalysts: Role of Copper Structure and Metal–Oxide Interface in Methanol Synthesis

DOE PAGES

Palomino, Robert M.; Ramirez, Pedro J.; Liu, Zongyuan; ...

2017-08-21

The results of kinetic tests and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) show the important role played by a ZnO–copper interface in the generation of CO and the synthesis of methanol from CO 2 hydrogenation. The deposition of nanoparticles of ZnO on Cu(100) and Cu(111), θ oxi < 0.3 monolayer, produces highly active catalysts. The catalytic activity of these systems increases in the sequence: Cu(111) < Cu(100) < ZnO/Cu(111) < ZnO/Cu(100). The structure of the copper substrate influences the catalytic performance of a ZnO–copper interface. Furthermore, size and metal–oxide interactions affect the chemical and catalytic properties of the oxide making themore » supported nanoparticles different from bulk ZnO. The formation of a ZnO–copper interface favors the binding and conversion of CO 2 into a formate intermediate that is stable on the catalyst surface up to temperatures above 500 K. Alloys of Zn with Cu(111) and Cu(100) were not stable at the elevated temperatures (500–600 K) used for the CO 2 hydrogenation reaction. However, reaction with CO 2 oxidized the zinc, enhancing its stability over the copper substrates.« less

Hydrogenation of CO 2 on ZnO/Cu(100) and ZnO/Cu(111) Catalysts: Role of Copper Structure and Metal–Oxide Interface in Methanol Synthesis

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

Palomino, Robert M.; Ramirez, Pedro J.; Liu, Zongyuan

The results of kinetic tests and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) show the important role played by a ZnO–copper interface in the generation of CO and the synthesis of methanol from CO 2 hydrogenation. The deposition of nanoparticles of ZnO on Cu(100) and Cu(111), θ oxi < 0.3 monolayer, produces highly active catalysts. The catalytic activity of these systems increases in the sequence: Cu(111) < Cu(100) < ZnO/Cu(111) < ZnO/Cu(100). The structure of the copper substrate influences the catalytic performance of a ZnO–copper interface. Furthermore, size and metal–oxide interactions affect the chemical and catalytic properties of the oxide making themore » supported nanoparticles different from bulk ZnO. The formation of a ZnO–copper interface favors the binding and conversion of CO 2 into a formate intermediate that is stable on the catalyst surface up to temperatures above 500 K. Alloys of Zn with Cu(111) and Cu(100) were not stable at the elevated temperatures (500–600 K) used for the CO 2 hydrogenation reaction. However, reaction with CO 2 oxidized the zinc, enhancing its stability over the copper substrates.« less

General purpose PDP-11 interface processor

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

Purtilo, J.

1982-10-01

The Z80 interface card, which for simplicity we refer to as the Zcard, is a general purpose microprocessor which is directly interfaced to the Whaley multiplexor, itself implemented on PDP-11 series computers at the University of Illinois. The Zcard provides two serial ports at EAI interface levels and contains up to 16K of local memory. The principle function of the Zcard is to serve as an interface in which the user might alter protocols, change interface characteristics (e.g. baud rate, hardware echo, or flow control), or switch between synchronous and asynchronous modes all under software control. In addition, the Zcardmore » provides extra lines for control of external devices (e.g. modem) and input of status data. In the simpliest use, the Zcard runs a program, downloaded from the PDP-11, which emulates the level EIAFB card (previously developed for the Whaley Multiplexor) for serial communication with terminals. Using no flow control, Zcard performance seems superior to that of the EIAFB card in that no characters are lost under normal use (due to the much larger buffer which the Zcard can provide). The Zcard can further distinguish itself from the EIAFB card in that flow control can be enabled by software. A more sophisticated application of the Zcard might include linking several Zcards (using a synchronous option and both of the provided ports) into a network. In this capacity, a ring topology suggests itself as the most immediate choice, although many alternate connection schemes can be envisioned. This report is intended to summarize the project as well as provide an outline for those intending to modify or program the Zcard.« less

An adaptive extended finite element method for the analysis of agglomeration of colloidal particles in a flowing fluid

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

Choi, Young Joon; Jorshari, Razzi Movassaghi; Djilali, Ned

2015-03-10

Direct numerical simulations of the flow-nanoparticle interaction in a colloidal suspension are presented using an extended finite element method (XFEM) in which the dynamics of the nanoparticles is solved in a fully-coupled manner with the flow. The method is capable of accurately describing solid-fluid interfaces without the need of boundary-fitted meshes to investigate the dynamics of particles in complex flows. In order to accurately compute the high interparticle shear stresses and pressures while minimizing computing costs, an adaptive meshing technique is incorporated with the fluid-structure interaction algorithm. The particle-particle interaction at the microscopic level is modeled using the Lennard-Jones (LJ)more » potential and the corresponding potential parameters are determined by a scaling procedure. The study is relevant to the preparation of inks used in the fabrication of catalyst layers for fuel cells. In this paper, we are particularly interested in investigating agglomeration of the nanoparticles under external shear flow in a sliding bi-periodic Lees-Edwards frame. The results indicate that the external shear has a crucial impact on the structure formation of colloidal particles in a suspension.« less

Readings on Managing Organizational Quality

DTIC Science & Technology

1990-05-01

Produc- tivify Review, Autumn, 1985. VI. Acknow ledg- Ishikawa , Kaoru . Guide to Quality Control. Tokyo: Asian Productivity Organization.m ents 1976. We are...indebted to many people for the develop- Ishikawa , Kaoru What is Total Quality Con- ment of the ideas expressed in this paper. Chief trol?: The...Developed by Kaoru Ishikawa , this di- Yes agram breaks the causes into general categories like methods. .............. materials, machines, and man, and

Steam Reforming of Methyl Fuel - Phase I

DTIC Science & Technology

1977-06-30

best catalyst . 2.0 TEST DESCRIPTION 2.1 Technical Background The basic reactions occurring in steam reforming of methanol are CH3OH + H20 CO2 + 3H 2...chamber contains the test catalyst . The fuel feed tank was filled with premixed methanol /gasoline mixture. Fuel flow as well as water flow were measured...carbon-oxygen bond formation and therefore follows a different mechanism than the methanol reaction . Different catalysts promote these types of

Development of GREET Catalyst Module

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

Wang, Zhichao; Dunn, Jennifer B.; Cronauer, Donald C.

2014-09-01

Catalysts are critical inputs for many pathways that convert biomass into biofuels. Energy consumption and greenhouse gas (GHG) emissions during the production of catalysts and chemical inputs influence the life-cycle energy consumption, and GHG emissions of biofuels and need to be considered in biofuel life-cycle analysis (LCA). In this report, we develop energy and material flows for the production of three different catalysts (tar reforming, alcohol synthesis, Zeolite Socony Mobil-5 [ZSM-5]) and two chemicals (olivine, dimethyl ether of polyethylene glycol [DEPG]). These compounds and catalysts are now included in the Greenhouse Gases, Regulated Emissions and Energy Use in Transportation (GREET™)more » catalyst module. They were selected because they are consumed in existing U.S. Department of Energy (DOE) analyses of biofuel processes. For example, a thermochemical ethanol production pathway (indirect gasification and mixed alcohol synthesis) developed by the National Renewable Energy Laboratory (NREL) uses olivine, DEPG, and tar reforming and alcohol synthesis catalysts (Dutta et al., 2011). ZSM-5 can be used in biofuel production pathways such as catalytic upgrading of sugars into hydrocarbons (Biddy and Jones, 2013). Other uses for these compounds and catalysts are certainly possible. In this report, we document the data sources and methodology we used to develop material and energy flows for the catalysts and compounds in the GREET catalyst module. In Section 2 we focus on compounds used in the model Dutta et al. (2011) developed. In Section 3, we report material and energy flows associated with ZSM-5 production. Finally, in Section 4, we report results.« less

Stability of a Bifunctional Cu-Based Core@Zeolite Shell Catalyst for Dimethyl Ether Synthesis Under Redox Conditions Studied by Environmental Transmission Electron Microscopy and In Situ X-Ray Ptychography.

PubMed

Baier, Sina; Damsgaard, Christian D; Klumpp, Michael; Reinhardt, Juliane; Sheppard, Thomas; Balogh, Zoltan; Kasama, Takeshi; Benzi, Federico; Wagner, Jakob B; Schwieger, Wilhelm; Schroer, Christian G; Grunwaldt, Jan-Dierk

2017-06-01

When using bifunctional core@shell catalysts, the stability of both the shell and core-shell interface is crucial for catalytic applications. In the present study, we elucidate the stability of a CuO/ZnO/Al2O3@ZSM-5 core@shell material, used for one-stage synthesis of dimethyl ether from synthesis gas. The catalyst stability was studied in a hierarchical manner by complementary environmental transmission electron microscopy (ETEM), scanning electron microscopy (SEM) and in situ hard X-ray ptychography with a specially designed in situ cell. Both reductive activation and reoxidation were applied. The core-shell interface was found to be stable during reducing and oxidizing treatment at 250°C as observed by ETEM and in situ X-ray ptychography, although strong changes occurred in the core on a 10 nm scale due to the reduction of copper oxide to metallic copper particles. At 350°C, in situ X-ray ptychography indicated the occurrence of structural changes also on the µm scale, i.e. the core material and parts of the shell undergo restructuring. Nevertheless, the crucial core-shell interface required for full bifunctionality appeared to remain stable. This study demonstrates the potential of these correlative in situ microscopy techniques for hierarchically designed catalysts.

Continuous preparation of carbon-nanotube-supported platinum catalysts in a flow reactor directly heated by electric current

PubMed Central

dos Santos, Antonio Rodolfo; Kunz, Ulrich; Turek, Thomas

2011-01-01

Summary In this contribution we present for the first time a continuous process for the production of highly active Pt catalysts supported by carbon nanotubes by use of an electrically heated tubular reactor. The synthesized catalysts show a high degree of dispersion and narrow distributions of cluster sizes. In comparison to catalysts synthesized by the conventional oil-bath method a significantly higher electrocatalytic activity was reached, which can be attributed to the higher metal loading and smaller and more uniformly distributed Pt particles on the carbon support. Our approach introduces a simple, time-saving and cost-efficient method for fuel cell catalyst preparation in a flow reactor which could be used at a large scale. PMID:22043252

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

Performance of Ni/dolomite pellet catalyst on gas distribution from cassava rhizome gasification with a modular fixed-bed gasifier.

PubMed

Sricharoenchaikul, V; Atong, D; Sornkade, P; Nisamaneenate, J

2017-05-01

Thermal conversion of cassava rhizome was performed using a modular downdraft gasifier with the addition of Ni-based catalysts as promising tar eliminating and produced gas upgrading techniques. The activities of a synthesized 5% Ni/dolomite pellet catalyst prepared by impregnation method were investigated in a secondary reactor downstream of the gasifier. High reforming activity of the Ni/dolomite pellet catalyst on tar reduction was achieved. The conversion to H 2 and CO was improved via steam reforming of methane and char reaction with CO 2 . Moreover, the formation of CH 4 and C x H y was diminished through the tar or condensable hydrocarbon reformed on the catalyst surface. The carbon and hydrogen conversions of cassava rhizome with prepared catalyst were 83.79% and 61.78%, respectively, at an air flow rate of 1.98 m 3 /hr. At this condition, tar formation was low, while the lower heating value was 4.39 MJ/m 3 and H 2 to CO molar ratio was 1.22. Generally, the addition of a catalyst not only enhanced gas production, but also reduced tar and particulate matter generation; thus, its implementation should help lessen the pollution control requirement and cost of operation, while allowing higher quality fuel gas production.

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

High-throughput screening of nanoparticle catalysts made by flame spray pyrolysis as hydrocarbon/NO oxidation catalysts.

PubMed

Weidenhof, B; Reiser, M; Stöwe, K; Maier, W F; Kim, M; Azurdia, J; Gulari, E; Seker, E; Barks, A; Laine, R M

2009-07-08

We describe here the use of liquid-feed flame spray pyrolysis (LF-FSP) to produce high surface area, nonporous, mixed-metal oxide nanopowders that were subsequently subjected to high-throughput screening to assess a set of materials for deNO(x) catalysis and hydrocarbon combustion. We were able to easily screen some 40 LF-FSP produced materials. LF-FSP produces nanopowders that very often consist of kinetic rather than thermodynamic phases. Such materials are difficult to access or are completely inaccessible via traditional catalyst preparation methods. Indeed, our studies identified a set of Ce(1-x)Zr(x)O(2) and Al(2)O(3)-Ce(1-x)Zr(x)O(2) nanopowders that offer surprisingly good activities for both NO(x) reduction and propane/propene oxidation both in high-throughput screening and in continuous flow catalytic studies. All of these catalysts offer activities comparable to traditional Pt/Al(2)O(3) catalysts but without Pt. Thus, although Pt-free, they are quite active for several extremely important emission control reactions, especially considering that these are only first generation materials. Indeed, efforts to dope the active catalysts with Pt actually led to lower catalytic activities. Thus the potential exists to completely change the materials used in emission control devices, especially for high-temperature reactions as these materials have already been exposed to 1500 degrees C; however, much research must be done before this potential is verified.

Optimization of information content in a mass spectrometry based flow-chemistry system by investigating different ionization approaches.

PubMed

Martha, Cornelius T; Hoogendoorn, Jan-Carel; Irth, Hubertus; Niessen, Wilfried M A

2011-05-15

Current development in catalyst discovery includes combinatorial synthesis methods for the rapid generation of compound libraries combined with high-throughput performance-screening methods to determine the associated activities. Of these novel methodologies, mass spectrometry (MS) based flow chemistry methods are especially attractive due to the ability to combine sensitive detection of the formed reaction product with identification of introduced catalyst complexes. Recently, such a mass spectrometry based continuous-flow reaction detection system was utilized to screen silver-adducted ferrocenyl bidentate catalyst complexes for activity in a multicomponent synthesis of a substituted 2-imidazoline. Here, we determine the merits of different ionization approaches by studying the combination of sensitive detection of product formation in the continuous-flow system with the ability to simultaneous characterize the introduced [ferrocenyl bidentate+Ag](+) catalyst complexes. To this end, we study the ionization characteristics of electrospray ionization (ESI), atmospheric-pressure chemical ionization (APCI), no-discharge APCI, dual ESI/APCI, and dual APCI/no-discharge APCI. Finally, we investigated the application potential of the different ionization approaches by the investigation of ferrocenyl bidentate catalyst complex responses in different solvents. Copyright © 2011 Elsevier B.V. All rights reserved.

40 CFR 65.162 - Nonflare control and recovery device monitoring records.

Code of Federal Regulations, 2010 CFR

2010-07-01

...). For catalytic incinerators, record the daily average of the temperature upstream of the catalyst bed and the daily average of the temperature differential across the bed. For halogen scrubbers, record... regeneration stream flow and carbon bed regeneration temperature are monitored, the following records shall be...

Temperature-programmed deoxygenation of acetic acid on molybdenum carbide catalysts

DOE PAGES

Nash, Connor P.; Farberow, Carrie A.; Hensley, Jesse E.

2017-02-07

Temperature programmed reaction (TPRxn) is a simple yet powerful tool for screening solid catalyst performance at a variety of conditions. A TPRxn system includes a reactor, furnace, gas and vapor sources, flow control, instrumentation to quantify reaction products (e.g., gas chromatograph), and instrumentation to monitor the reaction in real time (e.g., mass spectrometer). Here, we apply the TPRxn methodology to study molybdenum carbide catalysts for the deoxygenation of acetic acid, an important reaction among many in the upgrading/stabilization of biomass pyrolysis vapors. TPRxn is used to evaluate catalyst activity and selectivity and to test hypothetical reaction pathways (e.g., decarbonylation, ketonization,more » and hydrogenation). Furthermore, the results of the TPRxn study of acetic acid deoxygenation show that molybdenum carbide is an active catalyst for this reaction at temperatures above ca. 300 °C and that the reaction favors deoxygenation (i.e., C-O bond-breaking) products at temperatures below ca. 400 °C and decarbonylation (i.e., C-C bond-breaking) products at temperatures above ca. 400 °C.« less

Evaluation and characterization of the methane-carbon dioxide decomposition reaction

NASA Technical Reports Server (NTRS)

Davenport, R. J.; Schubert, F. H.; Shumar, J. W.; Steenson, T. S.

1975-01-01

A program was conducted to evaluate and characterize the carbon dioxide-methane (CO2-CH4) decomposition reaction, i.e., CO2 + CH4 = 2C + 2H2O. The primary objective was to determine the feasibility of applying this reaction at low temperatures as a technique for recovering the oxygen (O2) remaining in the CO2 which exits mixed with CH4 from a Sabatier CO2 reduction subsystem (as part of an air revitalization system of a manned spacecraft). A test unit was designed, fabricated, and assembled for characterizing the performance of various catalysts for the reaction and ultraviolet activation of the CH4 and CO2. The reactor included in the test unit was designed to have sufficient capacity to evaluate catalyst charges of up to 76 g (0.17 lb). The test stand contained the necessary instrumentation and controls to obtain the data required to characterize the performance of the catalysts and sensitizers tested: flow control and measurement, temperature control and measurement, product and inlet gas analysis, and pressure measurement. A product assurance program was performed implementing the concepts of quality control and safety into the program effort.

North Polar Cap Layers and Ledges

NASA Image and Video Library

2016-08-24

At the edge of Mars' permanent North Polar cap, we see an exposure of the internal layers, each with a different mix of water ice, dust and dirt. These layers are believed to correspond to different climate conditions over the past tens of thousands of years. When we zoom in closer, we see that the distinct layers erode differently. Some are stronger and more resistant to erosion, others only weakly cemented. The strong layers form ledges. http://photojournal.jpl.nasa.gov/catalog/PIA21022

Reconstructing western Grand Canyon's lava dams and their failure mechanisms: new insights from geochemical correlation and 40Ar/39Ar dating

NASA Astrophysics Data System (ADS)

Crow, R.; Karlstrom, K. E.; McIntosh, W. C.; Peters, L.; Dunbar, N. W.

2010-12-01

New geochemical analyzes and 40Ar/39Ar dating of lava dam remnants allows for the more accurate reconstruction of the timing, extent, and structure of western Grand Canyon’s lava dams. Whole-rock major, trace, and rare-earth element (REE) analyzes on over 60 basaltic lava dam remnants, cascades, plugs, and basaltic alluvium, show compositional variation from basanites to alkali basalts to tholeiites. Whitmore Canyon flows, for example, are some of the only tholeiitic flows and have a distinguishable trace and REE composition, which allows for correlation of dam remnants. Over 30 new high-precision 40Ar/39Ar dates also aid in remnant correlation and establish a better-constrained sequence of intra-canyon lava dams. Reliable 40Ar/39Ar dates on western Grand Canyon’s intra-canyon basalts range from ca. 100 ka to 840 ka (new date). The best understood lava dam formed from tholeiitic flows that erupted on the north rim, flowed down Whitmore side canyon and blocked a 6-km-long reach of the Grand Canyon. The youngest of these flows is unique because we know its age (200ka), its composition (tholeiitic), and the exact area where it entered Grand Canyon. The highest flow in the resulting dam, Whitmore Cascade, is capped with very coarse basaltic alluvium that previous workers have attributed to an upstream catastrophic dam failure event at about 200 ka. However, strong similarities between the geochemistry and age of the alluvium with the underlying Whitmore Cascade flow suggest that the alluvial deposit is related to failure of the 200 ka Whitmore Cascade dam itself. Similarly the 100 ka Upper Gray Ledge flow is commonly overlain by a balsaltic alluvium that is indistinguishable in terms of age and geochemistry from the underlying Upper Gray Ledge flow. These observations lead to a new model for Grand Canyon lava dams by which lava dams undergo multi-staged failure where the upstream parts of dams fail quickly (sometimes catastrophically) but downstream parts are longer lived because they undergo less interaction with river water and fracturing and generally fill dry portions of the river bed. Identification of far-traveled clasts on top of lava dam remnants in at least two locations supports the idea that the stable Colorado River established itself on top of the distal parts of some lava dams. Thus, whereas previous workers reported that deposits from outburst flood dam failure events exist in western grand canyon, our data identify specific dam failures and an interaction of catastrophic events at the head of lava dams and modified fluvial processes in distal portions of dams.

Oxidative Degradation of Methyl Orange Solution by Fe-MKSF Catalyst: Identification of Radical Species

NASA Astrophysics Data System (ADS)

Abdullah, N. H.; Selamat, M. K. A.; Nasuha, N.; Hassan, H.; Zubir, N. A.

2018-06-01

Iron–immobilized montmorillonite KSF (Fe-MKSF) has been recognized as promising catalyst in degrading persistence organic contaminants. However, detailed mechanistic insight during the catalysis which involving the formation and identification of radical species were remained indeterminate due to complex reaction. Inspiring by this gap, iron-immobilized clay (Fe-MKSF) was synthesized and used as heterogeneous catalyst in the oxidative degradation of methyl orange (MO) solution. Identification of radical species were determined through the inclusion of different types of radical scavenging agent during the Fenton-like reaction at optimum condition. Interestingly, dominant radical species were found to be hydroperoxyl radicals (•OOH) which subsequently followed by hydroxyl radicals (•OH) during the catalysis. Based on the percentage of MO removal, it was suggested that approximately 88% of the •OOH radicals existed at the interface of catalyst while 39% presence in bulk solution. Meanwhile, the interface •OH radicals promoted 38% of MO removal, whilst 4% by the bulk •OH radicals. Hence, these findings have conveyed novel insight on detailed radicals’ identification as well as its’ interaction during the catalysis.

Active CdS/rGO photocatalyst by a high temperature gas-solid reaction for hydrogen production by splitting of water

NASA Astrophysics Data System (ADS)

Singh, Arvind; Sinha, A. S. K.

2018-02-01

rGO supported CdS photocatalysts has been prepared by a two steps method, i.e. impregnation of GO/rGO with CdSO4 followed by a high temperature reaction with H2S gas. Activity of this catalyst was superior to a catalyst of same composition prepared by commonly reported hydrothermal technique. Detailed microstructure studies were carried out using FTIR, PL, DRS, XRD, TEM, SAED, TPO and XPS. A much greater chemical interaction at the interface of CdS and rGO and also a higher absorption of visible light were observed in the reported catalyst. It has been concluded that the high temperature reaction with H2S has imparted n-type semiconductivity to CdS which with p-type rGO and synergy of chemical interaction at the interface has resulted into formation of a p-n hetrojunction. The formation of hetrojunction and high electron mobility of rGO has given a superior activity due to an efficient charge separation to the catalyst prepared by the technique reported in this paper.

Carbon Nanotubes/Nanofibers by Plasma Enhanced Chemical Vapour Deposition

NASA Technical Reports Server (NTRS)

Teo, K. B. K.; Hash, D. B.; Bell, M. S.; Chhowalla, M.; Cruden, B. A.; Amaratunga, G. A. J.; Meyyappan, M.; Milne, W. I.

2005-01-01

Plasma enhanced chemical vapour deposition (PECVD) has been recently used for the production of vertically aligned carbon nanotubedfibers (CN) directly on substrates. These structures are potentially important technologically as electron field emitters (e.g. microguns, microwave amplifiers, displays), nanoelectrodes for sensors, filter media, superhydrophobic surfaces and thermal interface materials for microelectronics. A parametric study on the growth of CN grown by glow discharge dc-PECVD is presented. In this technique, a substrate containing thin film Ni catalyst is exposed to C2H2 and NH3 gases at 700 C. Without plasma, this process is essentially thermal CVD which produces curly spaghetti-like CN as seen in Fig. 1 (a). With the plasma generated by biasing the substrate at -6OOV, we observed that the CN align vertically during growth as shown in Fig. l(b), and that the magnitude of the applied substrate bias affects the degree of alignment. The thickness of the thin film Ni catalyst was found to determine the average diameter and inversely the length of the CN. The yield and density of the CN were controlled by the use of different diffusion barrier materials under the Ni catalyst. Patterned CN growth [Fig. l(c)], with la variation in CN diameter of 4.1% and 6.3% respectively, is achieved by lithographically defining the Ni thin film prior to growth. The shape of the structures could be varied from very straight nanotube-like to conical tip-like nanofibers by increasing the ratio of C2H2 in the gas flow. Due to the plasma decomposition of C2H2, amorphous carbon (a-C) is an undesirable byproduct which could coat the substrate during CN growth. Using a combination of depth profiled Auger electron spectroscopy to study the substrate and in-situ mass spectroscopy to examine gas phase neutrals and ions, the optimal conditions for a-C free growth of CN is determined.

Sealing in Turbomachinery

NASA Technical Reports Server (NTRS)

Chupp, Raymond E.; Hendricks, Robert C.; Lattime, Scott B.; Steinetz, Bruce M.

2006-01-01

Clearance control is of paramount importance to turbomachinery designers and is required to meet today's aggressive power output, efficiency, and operational life goals. Excessive clearances lead to losses in cycle efficiency, flow instabilities, and hot gas ingestion into disk cavities. Insufficient clearances limit coolant flows and cause interface rubbing, overheating downstream components and damaging interfaces, thus limiting component life. Designers have put renewed attention on clearance control, as it is often the most cost effective method to enhance system performance. Advanced concepts and proper material selection continue to play important roles in maintaining interface clearances to enable the system to meet design goals. This work presents an overview of turbomachinery sealing to control clearances. Areas covered include: characteristics of gas and steam turbine sealing applications and environments, benefits of sealing, types of standard static and dynamics seals, advanced seal designs, as well as life and limitations issues.

Modeling of axial vibrational control technique for CdTe VGF crystal growth under controlled cadmium partial pressure

NASA Astrophysics Data System (ADS)

Avetissov, I.; Kostikov, V.; Meshkov, V.; Sukhanova, E.; Grishechkin, M.; Belov, S.; Sadovskiy, A.

2014-01-01

A VGF growth setup assisted by axial vibrations of baffle submerged into CdTe melt with controlled Cd partial pressure was designed. An influence of baffle shape on flow velocity map, temperature distribution in CdTe melt and interface shape of growing crystal was analyzed by numerical simulation and physical modeling. To produce the desirable shape of crystal melt interface we slant under different angles vertical generatrix in a cylindrical disk and made chasing on faceplates of a disk. It was ascertained that a disk with conical generatrix formed more intensive convective flows from a faceplate with larger diameter. It was shown that at CdTe VGF crystal growth rate about 10 mm/h application of AVC technique made it possible to produce convex interface for 2 in. crystal diameter.

Exhaust gas purification system for lean burn engine

DOEpatents

Haines, Leland Milburn

2002-02-19

An exhaust gas purification system for a lean burn engine includes a thermal mass unit and a NO.sub.x conversion catalyst unit downstream of the thermal mass unit. The NO.sub.x conversion catalyst unit includes at least one catalyst section. Each catalyst section includes a catalytic layer for converting NO.sub.x coupled to a heat exchanger. The heat exchanger portion of the catalyst section acts to maintain the catalytic layer substantially at a desired temperature and cools the exhaust gas flowing from the catalytic layer into the next catalytic section in the series. In a further aspect of the invention, the exhaust gas purification system includes a dual length exhaust pipe upstream of the NO.sub.x conversion catalyst unit. The dual length exhaust pipe includes a second heat exchanger which functions to maintain the temperature of the exhaust gas flowing into the thermal mass downstream near a desired average temperature.

Shielded regeneration heating element for a particulate filter

DOEpatents

Gonze, Eugene V [Pinckney, MI; Ament, Frank [Troy, MI

2011-01-04

An exhaust system includes a particulate filter (PF) that is disposed downstream from an engine. The PF filters particulates within an exhaust from the engine. A heating element heats particulate matter in the PF. A catalyst substrate or a flow converter is disposed upstream from said heating element. The catalyst substrate oxidizes the exhaust prior to reception by the heating element. The flow converter converts turbulent exhaust flow to laminar exhaust flow prior to reception by the heating element.

Controllable synthesis of metal selenide heterostructures mediated by Ag2Se nanocrystals acting as catalysts

NASA Astrophysics Data System (ADS)

Zhou, Jiangcong; Huang, Feng; Xu, Ju; Wang, Yuansheng

2013-09-01

Ag2Se nanocrystals were demonstrated to be novel semiconductor mediators, or in other word catalysts, for the growth of semiconductor heterostructures in solution. This is a result of the unique feature of Ag2Se as a fast ion conductor, allowing foreign cations to dissolve and then to heterogrow the second phase. Using Ag2Se nanocrystals as catalysts, dimeric metal selenide heterostructures such as Ag2Se-CdSe and Ag2Se-ZnSe, and even multi-segment heterostructures such as Ag2Se-CdSe-ZnSe and Ag2Se-ZnSe-CdSe, were successfully synthesized. Several interesting features were found in the Ag2Se based heterogrowth. At the initial stage of heterogrowth, a layer of the second phase forms on the surface of an Ag2Se nanosphere, with a curved junction interface between the two phases. With further growth of the second phase, the Ag2Se nanosphere tends to flatten the junction surface by modifying its shape from sphere to hemisphere in order to minimize the conjunct area and thus the interfacial energy. Notably, the crystallographic relationship of the two phases in the heterostructure varies with the lattice parameters of the second phase, in order to reduce the lattice mismatch at the interface. Furthermore, a small lattice mismatch at the interface results in a straight rod-like second phase, while a large lattice mismatch would induce a tortuous product. The reported results may provide a new route for developing novel selenide semiconductor heterostructures which are potentially applicable in optoelectronic, biomedical, photovoltaic and catalytic fields.Ag2Se nanocrystals were demonstrated to be novel semiconductor mediators, or in other word catalysts, for the growth of semiconductor heterostructures in solution. This is a result of the unique feature of Ag2Se as a fast ion conductor, allowing foreign cations to dissolve and then to heterogrow the second phase. Using Ag2Se nanocrystals as catalysts, dimeric metal selenide heterostructures such as Ag2Se-CdSe and Ag2Se-ZnSe, and even multi-segment heterostructures such as Ag2Se-CdSe-ZnSe and Ag2Se-ZnSe-CdSe, were successfully synthesized. Several interesting features were found in the Ag2Se based heterogrowth. At the initial stage of heterogrowth, a layer of the second phase forms on the surface of an Ag2Se nanosphere, with a curved junction interface between the two phases. With further growth of the second phase, the Ag2Se nanosphere tends to flatten the junction surface by modifying its shape from sphere to hemisphere in order to minimize the conjunct area and thus the interfacial energy. Notably, the crystallographic relationship of the two phases in the heterostructure varies with the lattice parameters of the second phase, in order to reduce the lattice mismatch at the interface. Furthermore, a small lattice mismatch at the interface results in a straight rod-like second phase, while a large lattice mismatch would induce a tortuous product. The reported results may provide a new route for developing novel selenide semiconductor heterostructures which are potentially applicable in optoelectronic, biomedical, photovoltaic and catalytic fields. Electronic supplementary information (ESI) available: Fig. S1-S8 and Table S1. See DOI: 10.1039/c3nr03601d

Vapor-liquid-solid growth of silicon and silicon germanium nanowires

NASA Astrophysics Data System (ADS)

Nimmatoori, Pramod

2009-12-01

Si and Si1-xGex nanowires are promising materials with potential applications in various disciplines of science and technology. Small diameter nanowires can act as model systems to study interesting phenomena such as tunneling that occur in the nanometer regime. Furthermore, technical challenges in fabricating nanoscale size devices from thin films have resulted in interest and research on nanowires. In this perspective, vertical integrated nanowire field effect transistors (VINFETs) fabricated from Si nanowires are promising devices that offer better control on device properties and push the transistor architecture into the third dimension potentially enabling ultra-high transistor density circuits. Transistors fabricated from Si/Si 1-xGex nanowires have also been proposed that can have high carrier mobility. In addition, the Si and Si1-xGe x nanowires have potential to be used in various applications such as sensing, thermoelectrics and solar cells. Despite having considerable potential, the understanding of the vapor-liquid-solid (VLS) mechanism utilized to fabricate these wires is still rudimentary. Hence, the objective of this thesis is to understand the effects of nanoscale size and the role of catalyst that mediates the wire growth on the growth rate of Si and Si1-xGe x nanowires and interfacial abruptness in Si/Si1-xGe x axial heterostructure nanowires. Initially, the growth and structural properties of Si nanowires with tight diameter distribution grown from 10, 20 and 50 nm Au particles dispersed on a polymer-modified substrate was studied. A nanoparticle application process was developed to disperse Au particles on the substrate surface with negligible agglomeration and sufficient density. The growth temperature and SiH4 partial pressure were varied to optimize the growth conditions amenable to VLS growth with smooth wire morphology and negligible Si thin film deposition on wire sidewalls. The Si nanowire growth rate was studied as a function of growth time, temperature, SiH4 partial pressure and wire diameter and discussed in the context of the literature. The wire growth rate was found to increase with wire diameter in agreement with a size-related effect known as the Gibbs-Thomson effect. Subsequently, the effect of P and Sb doping on the growth rate and structural properties of Si nanowires was investigated. A reduction in wire growth rate was observed upon doping, which was pronounced in case of Sb doping, ascribable to P/Sb segregation at the vapor-liquid interface (catalyst surface) and the liquid-solid interface (growth front) that in turn reduces Si incorporation at these interfaces. The second part of thesis was focused on the Si1-xGe x alloy nanowires. The effect of wire diameter and growth conditions on the interfacial abruptness of Si/Si1-xGex heterostructure nanowires was examined. Abrupt interfaces were obtained at smaller wire diameters. However, the growth temperature wasn't found to have much impact on the interfacial abruptness. These results were explained in terms of catalyst effects on the interfacial abruptness. The remaining part of the study was focused on the effect of growth conditions on the growth rate of Si1-x Gex nanowires. It was found that the Si incorporation mechanism was different between Si and Si1-xGex nanowire growth which was ascribed to changes in the gas phase or catalyst composition that can impact the SiH4 decomposition kinetics at the catalyst surface (vapor-liquid interface) and/or Si incorporation at the growth front (liquid-solid interface).

A Matlab-Based Graphical User Interface for Simulation and Control Design of a Hydrogen Mixer

NASA Technical Reports Server (NTRS)

Richter, Hanz; Figueroa, Fernando

2003-01-01

A Graphical User Interface (GUI) that facilitates prediction and control design tasks for a propellant mixer is described. The Hydrogen mixer is used in rocket test stand operations at the NASA John C. Stennis Space Center. The mixer injects gaseous hydrogen (GH2) into a stream of liquid hydrogen (LH2) to obtain a combined flow with desired thermodynamic properties. The flows of GH2 and LH2 into the mixer are regulated by two control valves, and a third control valve is installed at the exit of the mixer to regulate the combined flow. The three valves may be simultaneously operated in order to achieve any desired combination of total flow, exit temperature and mixer pressure within the range of operation. The mixer, thus, constitutes a three-input, three-output system. A mathematical model of the mixer has been obtained and validated with experimental data. The GUI presented here uses the model to predict mixer response under diverse conditions.

Job-Grading System Manual for Nonappropriated Fund Instrumentalities

DTIC Science & Technology

1981-10-01

rationale for use and forwarded through designated channels to the office of DoD NAF Personnel Policy. E. USE OF OPM POSITION CLASSIFICATION AND JOB...marking, building and control of campfires, and identification of hazardous plants and animals. Schedules day or longer "camp-outs," publicizes the...Merchandisers PS-5 decorate designated areas, including showcases, ledges, and fixtures. Incumbents set up focal displays near entrances to attract cus

Novel 2D RuPt core-edge nanocluster catalyst for CO electro-oxidation

NASA Astrophysics Data System (ADS)

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

2015-10-01

A single layer, bi-metallic RuPt catalyst on Au(111) is synthesized using surface limited red-ox replacement of underpotentially deposited Cu and Pb monolayers though a two-step process. The resulting 2D RuPt monolayer nanoclusters have a unique core-edge structure with a Ru core and Pt at the edge along the perimeter. The activity of this catalyst is evaluated using CO monolayer oxidation as the probe reaction. Cyclic voltammetry demonstrates that the 2D RuPt core-edge catalyst morphology is significantly more active than either Pt or Ru monolayer catalysts. Density functional theory calculations in combination with infra-red spectroscopy data point towards oscillating variations (ripples) in the adsorption energy landscape along the radial direction of the Ru core as the origin of the observed behavior. Both, CO and OH experience a thermodynamic driving force for surface migration towards the Ru-Pt interface, where they adsorb most strongly and react rapidly. We propose that the complex interplay between epitaxial strain, ligand and finite size effects is responsible for the formation of the rippled RuPt monolayer cluster, which provides optimal conditions for a quasi-ideal bi-functional mechanism for CO oxidation, in which CO is adsorbed mainly on Pt, and Ru provides OH to the active Pt-Ru interface.

X-ray absorption spectroscopy using a self-seeded soft X-ray free-electron laser

DOE PAGES

Kroll, Thomas; Kern, Jan; Kubin, Markus; ...

2016-09-19

X-ray free electron lasers (XFELs) enable unprecedented new ways to study the electronic structure and dynamics of transition metal systems. L-edge absorption spectroscopy is a powerful technique for such studies and the feasibility of this method at XFELs for solutions and solids has been demonstrated. But, the required x-ray bandwidth is an order of magnitude narrower than that of self-amplified spontaneous emission (SASE), and additional monochromatization is needed. We compare L-edge x-ray absorption spectroscopy (XAS) of a prototypical transition metal system based on monochromatizing the SASE radiation of the linac coherent light source (LCLS) with a new technique based onmore » self-seeding of LCLS. We demonstrate how L-edge XAS can be performed using the self-seeding scheme without the need of an additional beam line monochromator. Lastly, we show how the spectral shape and pulse energy depend on the undulator setup and how this affects the x-ray spectroscopy measurements.« less

Ring current impoundment of the Io plasma torus

NASA Technical Reports Server (NTRS)

Siscoe, G. L.; Thorne, R. M.; Richardson, J. D.; Bagenal, F.; Sullivan, J. D.; Eviatar, A.

1981-01-01

A newly discovered feature in the Io plasma formation that may be described as a ramp separating a high-density plasma ledge on its Jupiterward side from the lower-density radially distended Io plasma disc on its anti-Jupiterward side is observed to coincide with a marked inward decrease in the ring current population. The spatial congruency of the counter-directed maximal gradients in both plasma bodies reveals a profound coupling between them. The existence of the ramp requires a local order-of-magnitude reduction in the diffusion coefficient that governs radial mass transport. It is demonstrated that the diminished diffusive efficiency there is caused by strong pressure gradient inhibition of the interchange instability that underlies mass transport. The Io plasma torus, which is defined as the region of strong ultraviolet emissions, is identified as the plasma ledge. The plasma density in the ledge is high and, incidentally therefore, able to emit strongly because it is impounded against rapid, centrifugal expulsion by the inwardly directed pressure of the ring current at its inner edge.

X-ray absorption spectroscopy using a self-seeded soft X-ray free-electron laser

PubMed Central

Kroll, Thomas; Kern, Jan; Kubin, Markus; Ratner, Daniel; Gul, Sheraz; Fuller, Franklin D.; Löchel, Heike; Krzywinski, Jacek; Lutman, Alberto; Ding, Yuantao; Dakovski, Georgi L.; Moeller, Stefan; Turner, Joshua J.; Alonso-Mori, Roberto; Nordlund, Dennis L.; Rehanek, Jens; Weniger, Christian; Firsov, Alexander; Brzhezinskaya, Maria; Chatterjee, Ruchira; Lassalle-Kaiser, Benedikt; Sierra, Raymond G.; Laksmono, Hartawan; Hill, Ethan; Borovik, Andrew; Erko, Alexei; Föhlisch, Alexander; Mitzner, Rolf; Yachandra, Vittal K.; Yano, Junko; Wernet, Philippe; Bergmann, Uwe

2016-01-01

X-ray free electron lasers (XFELs) enable unprecedented new ways to study the electronic structure and dynamics of transition metal systems. L-edge absorption spectroscopy is a powerful technique for such studies and the feasibility of this method at XFELs for solutions and solids has been demonstrated. However, the required x-ray bandwidth is an order of magnitude narrower than that of self-amplified spontaneous emission (SASE), and additional monochromatization is needed. Here we compare L-edge x-ray absorption spectroscopy (XAS) of a prototypical transition metal system based on monochromatizing the SASE radiation of the linac coherent light source (LCLS) with a new technique based on self-seeding of LCLS. We demonstrate how L-edge XAS can be performed using the self-seeding scheme without the need of an additional beam line monochromator. We show how the spectral shape and pulse energy depend on the undulator setup and how this affects the x-ray spectroscopy measurements. PMID:27828320

Understanding the Oxygen Evolution Reaction Mechanism on CoO x using Operando Ambient-Pressure X-ray Photoelectron Spectroscopy

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

Favaro, Marco; Yang, Jinhui; Nappini, Silvia

Photoelectrochemical water splitting is a promising approach for renewable production of hydrogen from solar energy and requires interfacing advanced water-splitting catalysts with semiconductors. Understanding the mechanism of function of such electrocatalysts at the atomic scale and under realistic working conditions is a challenging, yet important, task for advancing efficient and stable function. This is particularly true for the case of oxygen evolution catalysts and, here, we study a highly active Co 3O 4/Co(OH) 2 biphasic electrocatalyst on Si by means of operando ambient-pressure X-ray photoelectron spectroscopy performed at the solid/liquid electrified interface. Spectral simulation and multiplet fitting reveal that themore » catalyst undergoes chemical-structural transformations as a function of the applied anodic potential, with complete conversion of the Co(OH) 2 and partial conversion of the spinel Co 3O 4 phases to CoO(OH) under precatalytic electrochemical conditions. Furthermore, we observe new spectral features in both Co 2p and O 1s core-level regions to emerge under oxygen evolution reaction conditions on CoO(OH). The operando photoelectron spectra support assignment of these newly observed features to highly active Co 4+ centers under catalytic conditions. Comparison of these results to those from a pure phase spinel Co 3O 4 catalyst supports this interpretation and reveals that the presence of Co(OH) 2 enhances catalytic activity by promoting transformations to CoO(OH). The direct investigation of electrified interfaces presented in this work can be extended to different materials under realistic catalytic conditions, thereby providing a powerful tool for mechanism discovery and an enabling capability for catalyst design.« less

Understanding the Oxygen Evolution Reaction Mechanism on CoO x using Operando Ambient-Pressure X-ray Photoelectron Spectroscopy

DOE PAGES

Favaro, Marco; Yang, Jinhui; Nappini, Silvia; ...

2017-06-09

Photoelectrochemical water splitting is a promising approach for renewable production of hydrogen from solar energy and requires interfacing advanced water-splitting catalysts with semiconductors. Understanding the mechanism of function of such electrocatalysts at the atomic scale and under realistic working conditions is a challenging, yet important, task for advancing efficient and stable function. This is particularly true for the case of oxygen evolution catalysts and, here, we study a highly active Co 3O 4/Co(OH) 2 biphasic electrocatalyst on Si by means of operando ambient-pressure X-ray photoelectron spectroscopy performed at the solid/liquid electrified interface. Spectral simulation and multiplet fitting reveal that themore » catalyst undergoes chemical-structural transformations as a function of the applied anodic potential, with complete conversion of the Co(OH) 2 and partial conversion of the spinel Co 3O 4 phases to CoO(OH) under precatalytic electrochemical conditions. Furthermore, we observe new spectral features in both Co 2p and O 1s core-level regions to emerge under oxygen evolution reaction conditions on CoO(OH). The operando photoelectron spectra support assignment of these newly observed features to highly active Co 4+ centers under catalytic conditions. Comparison of these results to those from a pure phase spinel Co 3O 4 catalyst supports this interpretation and reveals that the presence of Co(OH) 2 enhances catalytic activity by promoting transformations to CoO(OH). The direct investigation of electrified interfaces presented in this work can be extended to different materials under realistic catalytic conditions, thereby providing a powerful tool for mechanism discovery and an enabling capability for catalyst design.« less

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

Nash, Connor P.; Farberow, Carrie A.; Hensley, Jesse E.

Temperature programmed reaction (TPRxn) is a simple yet powerful tool for screening solid catalyst performance at a variety of conditions. A TPRxn system includes a reactor, furnace, gas and vapor sources, flow control, instrumentation to quantify reaction products (e.g., gas chromatograph), and instrumentation to monitor the reaction in real time (e.g., mass spectrometer). Here, we apply the TPRxn methodology to study molybdenum carbide catalysts for the deoxygenation of acetic acid, an important reaction among many in the upgrading/stabilization of biomass pyrolysis vapors. TPRxn is used to evaluate catalyst activity and selectivity and to test hypothetical reaction pathways (e.g., decarbonylation, ketonization,more » and hydrogenation). Furthermore, the results of the TPRxn study of acetic acid deoxygenation show that molybdenum carbide is an active catalyst for this reaction at temperatures above ca. 300 °C and that the reaction favors deoxygenation (i.e., C-O bond-breaking) products at temperatures below ca. 400 °C and decarbonylation (i.e., C-C bond-breaking) products at temperatures above ca. 400 °C.« less

Constructing hierarchical interfaces: TiO 2-supported PtFe-FeO x nanowires for room temperature CO oxidation

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

Zhu, Huiyuan; Wu, Zili; Dong, Su

2015-08-05

This is a report of a facile approach to constructing catalytic active hierarchical interfaces in one-dimensional (1D) nanostructure, exemplified by the synthesis of TiO 2-supported PtFe–FeO x nanowires (NWs). The hierarchical interface, constituting atomic level interactions between PtFe and FeO x within each NW and the interactions between NWs and support (TiO 2), enables CO oxidation with 100% conversion at room temperature. We identify the role of the two interfaces by probing the CO oxidation reaction with isotopic labeling experiments. Both the oxygen atoms (Os) in FeO x and TiO 2 participate in the initial CO oxidation, facilitating the reactionmore » through a redox pathway. Moreover, the intact 1D structure leads to the high stability of the catalyst. After 30 h in the reaction stream, the PtFe–FeO x/TiO2 catalyst exhibits no activity decay. These results provide a general approach and new insights into the construction of hierarchical interfaces for advanced catalysis.« less

Process optimization for microcystin-LR degradation by Response Surface Methodology and mechanism analysis in gas-liquid hybrid discharge system.

PubMed

Zhang, Yi; Wei, Hanyu; Xin, Qing; Wang, Mingang; Wang, Qi; Wang, Qiang; Cong, Yanqing

2016-12-01

A gas-liquid hybrid discharge system was applied to microcystin-LR (MC-LR) degradation. MC-LR degradation was completed after 1 min under a pulsed high voltage of 16 kV, gas-liquid interface gap of 10 mm and oxygen flow rate of 160 L/h. The Box-Behnken Design was proposed in Response Surface Methodology to evaluate the influence of pulsed high voltage, electrode distance and oxygen flow rate on MC-LR removal efficiency. Multiple regression analysis, focused on multivariable factors, was employed and a reduced cubic model was developed. The ANOVA analysis shows that the model is significant and the model prediction on MC-LR removal was also validated with experimental data. The optimum conditions for the process are obtained at pulsed voltage of 16 kV, gas-liquid interface gap of 10 mm and oxygen flow rate of 120 L/h with ta removal efficiency of MC-LR of 96.6%. The addition of catalysts (TiO 2 or Fe 2+ ) in the gas-liquid hybrid discharge system was found to enhance the removal of MC-LR. The intermediates of MC-LR degradation were analyzed by liquid chromatography/mass spectrometry. The degradation pathway proposed envisaged the oxidation of hydroxyl radicals and ozone, and attack of high-energy electrons on the unsaturated double bonds of Adda and Mdha, with MC-LR finally decomposing into small molecular products. Copyright © 2016 Elsevier Ltd. All rights reserved.

Charge and Spin-State Characterization of Cobalt Bis( o-dioxolene) Valence Tautomers Using Co Kβ X-ray Emission and L-Edge X-ray Absorption Spectroscopies

DOE PAGES

Liang, H. Winnie; Kroll, Thomas; Nordlund, Dennis; ...

2016-12-30

The valence tautomeric states of Co(phen)(3,5-DBQ) 2 and Co(tmeda)(3,5-DBQ) 2, where 3,5-DBQ is either the semiquinone (SQ –) or catecholate (Cat 2–) form of 3,5-di- tert-butyl-1,2-benzoquinone, have been examined by a series of cobalt-specific X-ray spectroscopies. In this work, we have utilized the sensitivity of 1s3p X-ray emission spectroscopy (Kβ XES) to the oxidation and spin states of 3d transition-metal ions to determine the cobalt-specific electronic structure of valence tautomers. A comparison of their Kβ XES spectra with the spectra of cobalt coordination complexes with known oxidation and spin states demonstrates that the low-temperature valence tautomer can be described asmore » a low-spin Co III configuration and the high-temperature valence tautomer as a high-spin Co II configuration. This conclusion is further supported by Co L-edge X-ray absorption spectroscopy (L-edge XAS) of the high-temperature valence tautomers and ligand-field atomic-multiplet calculations of the Kβ XES and L-edge XAS spectra. In conclusion, the nature and strength of the magnetic exchange interaction between the cobalt center and SQ – in cobalt valence tautomers is discussed in view of the effective spin at the Co site from Kβ XES and the molecular spin moment from magnetic susceptibility measurements.« less

Charge and Spin-State Characterization of Cobalt Bis( o-dioxolene) Valence Tautomers Using Co Kβ X-ray Emission and L-Edge X-ray Absorption Spectroscopies

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

Liang, H. Winnie; Kroll, Thomas; Nordlund, Dennis

The valence tautomeric states of Co(phen)(3,5-DBQ) 2 and Co(tmeda)(3,5-DBQ) 2, where 3,5-DBQ is either the semiquinone (SQ –) or catecholate (Cat 2–) form of 3,5-di- tert-butyl-1,2-benzoquinone, have been examined by a series of cobalt-specific X-ray spectroscopies. In this work, we have utilized the sensitivity of 1s3p X-ray emission spectroscopy (Kβ XES) to the oxidation and spin states of 3d transition-metal ions to determine the cobalt-specific electronic structure of valence tautomers. A comparison of their Kβ XES spectra with the spectra of cobalt coordination complexes with known oxidation and spin states demonstrates that the low-temperature valence tautomer can be described asmore » a low-spin Co III configuration and the high-temperature valence tautomer as a high-spin Co II configuration. This conclusion is further supported by Co L-edge X-ray absorption spectroscopy (L-edge XAS) of the high-temperature valence tautomers and ligand-field atomic-multiplet calculations of the Kβ XES and L-edge XAS spectra. In conclusion, the nature and strength of the magnetic exchange interaction between the cobalt center and SQ – in cobalt valence tautomers is discussed in view of the effective spin at the Co site from Kβ XES and the molecular spin moment from magnetic susceptibility measurements.« less

Control of interface shape during high melting sesquioxide crystal growth by HEM technique

NASA Astrophysics Data System (ADS)

Hu, Kaiwei; Zheng, Lili; Zhang, Hui

2018-02-01

During crystal growth in heat exchanger method (HEM) system, the shape of the growth interface changes with the proceeding of the growth process, which limits the crystal size and reduces the quality of the crystal. In this paper, a modified HEM system is proposed to control the interface shape for growth of sesquioxide crystals. Numerical simulation is performed to predict heat transfer, melt flow and interface shape during growth of high melting sesquioxide crystals by the heat exchanger method. The results show that a flat or slightly convex interface shape is beneficial to reduce the solute pileup in front of the melt/crystal interface and decrease the radial temperature gradient inside the crystal during growth of sesquioxide crystals. The interface shape can be controlled by adjusting the gap size d and lower resistance heater power during growth. The growth rate and the melt/crystal interface position can be obtained by two measured temperatures.

High-temperature morphological evolution of lithographically introduced cavities in silicon carbide

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

Narushima, Takayuki; Glaeser, Andreas M.

2000-12-01

Internal cavities of controlled geometry and crystallography were introduced in 6H silicon carbide single crystals by combining lithographic methods, ion beam etching, and solid-state diffusion bonding. The morphological evolution of these internal cavities (negative crystals) in response to anneals of up to 128 h duration at 1900 degrees C was examined using optical microscopy. Surface energy anisotropy and faceting have a strong influence on both the geometric and kinetic characteristics of evolution. Decomposition of 12{bar 1}0 cavity edges into 101{bar 0} facets was observed after 16 h anneals, indicating that 12{bar 1}0 faces are not components of the Wulff shape.more » The shape evolution kinetics of penny-shaped cavities were also investigated. Experimentally observed evolution rates decreased much more rapidly with those predicted by a model in which surface diffusion is assumed to be rate-limiting. This suggests that the development of facets, and the associated loss of ledges and terraces during the initial stages of evolution results in an evolution process limited by the nucleation rate of attachment/detachment sites (ledges) on the facets.« less

Elucidation of reaction mechanism for m -cresol hydrodeoxygenation over Fe based catalysts: A kinetic study

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

Hong, Yongchun; Wang, Yong

Fe based catalysts are promising for hydrodeoxygenation (HDO) of lignin derived phenolics due to their high selectivity for aromatics. In this work, the reaction mechanism of m-cresol HDO on Fe catalysts and the kinetic consequence with Pd addition were elucidated by examining the effect of H2, H2O and m-cresol pressures on toluene formation rate on Fe and PdFe catalysts. A direct CO bond cleavage mechanism is proposed for HDO catalysis on both Fe and PdFe catalysts, while Pd provides a facilitated reaction pathway at the PdFe interface and therefore promotes the catalysis on Fe without changing the high selectivity towardsmore » aromatics.« less

Highly active catalytic Ru/TiO2 nanomaterials for continuous flow production of γ-valerolactone.

PubMed

Ouyang, Weiyi; Munoz-Batista, Mario; Fernandez-Garcia, Marcos; Luque, Rafael

2018-05-29

Green energy production from renewable sources is an attractive but challenging topic to face the likely energy crisis scenario in the future. In the current work, a series of versatile Ru/TiO2 catalysts were simply synthesized and employed in continuous flow catalytic transfer hydrogenation of industrially derived methyl levulinate biowaste (from Avantium Chemicals B.V.) to γ-valerolactone. Different analytical techniques were applied in the characterization of the as-synthesized catalysts, including XRD, SEM, EDX, TEM and XPS etc. The effects of various reaction conditions (e.g. temperature, concentration and flow rate) were investigated. Results suggested that optimum dispersion and distribution of Ru on the TiO2 surface could efficiently promote production of γ-valerolactone, with 5% Ru/TiO2 catalyst providing excelling catalytic performance and stability as compared to commercial Ru catalysts. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Methods for dehydration of sugars and sugar alcohols

DOEpatents

Holladay, Johnathan E [Kennewick, WA; Hu, Jianli [Kennewick, WA; Zhang, Xinjie [Burlington, MA; Wang, Yong [Richland, WA

2010-08-10

The invention includes a method of dehydration of a sugar using a dehydration catalyst and a co-catalyst within a reactor. A sugar is introduced and H.sub.2 is flowed through the reactor at a pressure of less than or equal to about 300 psig to convert at least some of the sugar into an anhydrosugar product. The invention includes a process for producing isosorbide. A starting material comprising sorbitol is flowed into a reactor. H.sub.2 is counter flowed through the reactor. The starting material is exposed to a catalyst in the presence of a co-catalyst which comprises at least one metal. The exposing is conducted at a hydrogen pressure of less than or equal to 300 psig within the reactor and the hydrogen removes at least some of any water present during the exposing and inhibits formation of colored byproducts.

High efficiency stoichiometric internal combustion engine system

DOEpatents

Winsor, Richard Edward; Chase, Scott Allen

2009-06-02

A power system including a stoichiometric compression ignition engine in which a roots blower is positioned in the air intake for the engine to control air flow. Air flow is decreased during part power conditions to maintain the air-fuel ratio in the combustion chamber of the engine at stoichiometric, thus enabling the use of inexpensive three-way catalyst to reduce oxides of nitrogen. The roots blower is connected to a motor generator so that when air flow is reduced, electrical energy is stored which is made available either to the roots blower to temporarily increase air flow or to the system electrical load and thus recapture energy that would otherwise be lost in reducing air flow.

Role of mixed boundaries on flow in open capillary channels with curved air-water interfaces.

PubMed

Zheng, Wenjuan; Wang, Lian-Ping; Or, Dani; Lazouskaya, Volha; Jin, Yan

2012-09-04

Flow in unsaturated porous media or in engineered microfluidic systems is dominated by capillary and viscous forces. Consequently, flow regimes may differ markedly from conventional flows, reflecting strong interfacial influences on small bodies of flowing liquids. In this work, we visualized liquid transport patterns in open capillary channels with a range of opening sizes from 0.6 to 5.0 mm using laser scanning confocal microscopy combined with fluorescent latex particles (1.0 μm) as tracers at a mean velocity of ∼0.50 mm s(-1). The observed velocity profiles indicate limited mobility at the air-water interface. The application of the Stokes equation with mixed boundary conditions (i.e., no slip on the channel walls and partial slip or shear stress at the air-water interface) clearly illustrates the increasing importance of interfacial shear stress with decreasing channel size. Interfacial shear stress emerges from the velocity gradient from the adjoining no-slip walls to the center where flow is trapped in a region in which capillary forces dominate. In addition, the increased contribution of capillary forces (relative to viscous forces) to flow on the microscale leads to increased interfacial curvature, which, together with interfacial shear stress, affects the velocity distribution and flow pattern (e.g., reverse flow in the contact line region). We found that partial slip, rather than the commonly used stress-free condition, provided a more accurate description of the boundary condition at the confined air-water interface, reflecting the key role that surface/interface effects play in controlling flow behavior on the nanoscale and microscale.

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

DOE PAGES

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

2016-05-09

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

Development of a preprototype sabatier CO2 reduction subsystem

NASA Technical Reports Server (NTRS)

Kleiner, G. N.; Birbara, P.

1980-01-01

A preoprototype Sabatier CO2 Reduction Subsystem was successfully designed, fabricated and tested. The lightweight, quick starting reactor utilizes a highly active and physically durable methanation catalyst composed of ruthenium on alumina. The use of this improved catalyst permits a single straight through plug flow design with an average lean component H2/CO2 conversion efficiency of over 99% over a range of H2/CO2 molar ratios of 1.8 to 5 while operating with flows equivalent to a crew size of one person steadystate to 3 persons cyclical (equivalent to 5 persons steady state). The reactor requires no heater operation after start-up even during simulated 55 minute lightside/39 minute darkside orbital operation over the above range of molar ratios and crew loadings. The subsystem's operation and performance is controlled by a microprocessor and displayed on a nineteen inch multi-colored cathode ray tube.

Development of a preprototype Sabatier CO2 reduction subsystem

NASA Technical Reports Server (NTRS)

Kleiner, G. N.; Birbara, P.

1981-01-01

A lightweight, quick starting reactor utilizes a highly active and physically durable methanation catalyst composed of ruthenium on alumina. The use of this improved catalyst permits a single straight through plug flow design with an average lean component H2/CO2 conversion efficiency of over 99% over a range of H2/CO2 molar ratios of 1.8 to 5 while operating with flows equivalent to a crew size of one person steadystate to 3 persons cyclical. The reactor requires no heater operation after start-up even during simulated 55 minute lightside/39 minute darkside orbital operation over the above range of molar ratios and crew loadings. Subsystem performance was proven by parametric testing and endurance testing over a wide range of crew sizes and metabolic loadings. The subsystem's operation and performance is controlled by a microprocessor and displayed on a nineteen inch multi-colored cathode ray tube.

Pt Catalyst Degradation in Aqueous and Fuel Cell Environments studied via In-Operando Anomalous Small-Angle X-ray Scattering

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

Gilbert, James A.; Kariuki, Nancy N.; Wang, Xiaoping

2015-08-01

The evolution of Pt nanoparticle cathode electrocatalyst size distribution in a polymer electrolyte membrane fuel cell (PEMFC) was followed during accelerated stress tests using in-operando anomalous small-angle X-ray scattering (ASAXS). This evolution was compared to that observed in an aqueous electrolyte environment using stagnant electrolyte, flowing electrolyte, and flowing electrolyte at elevated temperature to reveal the different degradation trends in the PEMFC and aqueous environments and to determine the relevance of aqueous measurements to the stability of Pt nanoparticle catalyst in the fuel cell environment. The observed changes in the particle size distributions (PSDs) were analyzed to elucidate the extentmore » and mechanisms of particle growth and corresponding mass and active surface area losses in the different environments. These losses indicate a Pt nanoparticle surface area loss mechanism controlled by Pt dissolution, the particle size dependence of Pt dissolution, the loss of dissolved Pt into the membrane and electrolyte, and, to a lesser extent, the re-deposition of dissolved Pt onto larger particles. Based on the geometric surface area loss, mass loss, and mean particle size increase trends, the aqueous environment best reflecting the fuel cell environment was found to be one in which the electrolyte is flowing rather than stagnant. Pt nanoparticle surface area loss resulting from potential cycling can be inhibited by reducing the number of particles smaller than a critical particle diameter (CPD), which was found to be similar to 3.5 to similar to 4 nm, with the CPD dependent on both the cycling protocol (square wave vs triangle wave) and the catalyst environment (fuel cell, aqueous stagnant, aqueous flowing electrolyte, or elevated temperature flowing electrolyte)« less

Invasive predator tips the balance of symmetrical competition between native coral-reef fishes.

PubMed

Kindinger, Tye L

2018-04-01

The importance of competition and predation in structuring ecological communities is typically examined separately such that interactions between these processes are seldom understood. By causing large reductions in native prey, invasive predators may modify native species interactions. I conducted a manipulative field experiment in The Bahamas to investigate the possibility that the invasive Pacific red lionfish (Pterois volitans) alters competition between planktivorous fairy and blackcap basslets (Gramma loreto and Gramma melacara, respectively). Competition between these coral-reef fishes is known to have symmetrical effects on the juveniles of both species, whereby the feeding positions under reef ledges and growth rates of these individuals are hindered. Following baseline censuses of local populations of competing basslets, I simultaneously manipulated the abundance of lionfish on entire reefs, and the abundance of basslets in local populations under isolated ledges within each reef, resulting in three treatments: unmanipulated control populations of both basslets, reduced abundance of fairy basslet, and reduced abundance of blackcap basslet. For eight weeks, I measured the change in biomass and feeding position of 2-5 cm size classes of each basslet species and calculated the growth rates of ~2 cm individuals using a standard mark-and-recapture method. Experimental populations were filmed at dusk using automated video cameras to quantify the behavior of lionfish overlapping with basslets. Video playback revealed lionfish hunted across all ledge positions, regardless of which basslet species were present, yet lionfish differentially reduced the biomass of only juvenile (2 cm) fairy basslet. Predation reduced the effects of interspecific competition on juvenile blackcap basslet as evidenced by corresponding shifts in feeding position toward coveted front edges of ledges and increases in growth rates that were comparable to the response of these fish in populations where competition was experimentally reduced. Thus, an invasive marine predator altered the outcome of interspecific competition via differential predation, which tipped the balance of competition between native prey species from symmetrical to asymmetrical effects on juveniles. This study reveals a newly demonstrated context in which predation can indirectly facilitate prey, further broadening our understanding of the interactive effects of predation and competition in the context of invasive species. © 2018 by the Ecological Society of America.

Unlocking the potential of supported liquid phase catalysts with supercritical fluids: low temperature continuous flow catalysis with integrated product separation

PubMed Central

Franciò, Giancarlo; Hintermair, Ulrich; Leitner, Walter

2015-01-01

Solution-phase catalysis using molecular transition metal complexes is an extremely powerful tool for chemical synthesis and a key technology for sustainable manufacturing. However, as the reaction complexity and thermal sensitivity of the catalytic system increase, engineering challenges associated with product separation and catalyst recovery can override the value of the product. This persistent downstream issue often renders industrial exploitation of homogeneous catalysis uneconomical despite impressive batch performance of the catalyst. In this regard, continuous-flow systems that allow steady-state homogeneous turnover in a stationary liquid phase while at the same time effecting integrated product separation at mild process temperatures represent a particularly attractive scenario. While continuous-flow processing is a standard procedure for large volume manufacturing, capitalizing on its potential in the realm of the molecular complexity of organic synthesis is still an emerging area that requires innovative solutions. Here we highlight some recent developments which have succeeded in realizing such systems by the combination of near- and supercritical fluids with homogeneous catalysts in supported liquid phases. The cases discussed exemplify how all three levels of continuous-flow homogeneous catalysis (catalyst system, separation strategy, process scheme) must be matched to locate viable process conditions. PMID:26574523

Unlocking the potential of supported liquid phase catalysts with supercritical fluids: low temperature continuous flow catalysis with integrated product separation.

PubMed

Franciò, Giancarlo; Hintermair, Ulrich; Leitner, Walter

2015-12-28

Solution-phase catalysis using molecular transition metal complexes is an extremely powerful tool for chemical synthesis and a key technology for sustainable manufacturing. However, as the reaction complexity and thermal sensitivity of the catalytic system increase, engineering challenges associated with product separation and catalyst recovery can override the value of the product. This persistent downstream issue often renders industrial exploitation of homogeneous catalysis uneconomical despite impressive batch performance of the catalyst. In this regard, continuous-flow systems that allow steady-state homogeneous turnover in a stationary liquid phase while at the same time effecting integrated product separation at mild process temperatures represent a particularly attractive scenario. While continuous-flow processing is a standard procedure for large volume manufacturing, capitalizing on its potential in the realm of the molecular complexity of organic synthesis is still an emerging area that requires innovative solutions. Here we highlight some recent developments which have succeeded in realizing such systems by the combination of near- and supercritical fluids with homogeneous catalysts in supported liquid phases. The cases discussed exemplify how all three levels of continuous-flow homogeneous catalysis (catalyst system, separation strategy, process scheme) must be matched to locate viable process conditions. © 2015 The Authors.

The conversion of biomass to light olefins on Fe-modified ZSM-5 catalyst: Effect of pyrolysis parameters.

PubMed

Zhang, Shihong; Yang, Mingfa; Shao, Jingai; Yang, Haiping; Zeng, Kuo; Chen, Yingquan; Luo, Jun; Agblevor, Foster A; Chen, Hanping

2018-07-01

Light olefins are the key building blocks for the petrochemical industry. In this study, the effects of in-situ and ex-situ process, temperature, Fe loading, catalyst to feed ratio and gas flow rate on the olefins carbon yield and selectivity were explored. The results showed that Fe-modified ZSM-5 catalyst increased the olefins yield significantly, and the ex-situ process was much better than in-situ. With the increasing of temperature, Fe-loading amount, catalyst to feed ratio, and gas flow rate, the carbon yields of light olefins were firstly increased and further decreased. The maximum carbon yield of light olefins (6.98% C-mol) was obtained at the pyrolysis temperature of 600°C, catalyst to feed ratio of 2, gas flow rate of 100ml/min, and 3wt% Fe/ZSM-5 for cellulose. The selectivity of C 2 H 4 was more than 60% for all feedstock, and the total light olefins followed the decreasing order of cellulose, corn stalk, hemicelluloses and lignin. Copyright © 2018 Elsevier B.V. All rights reserved.

Highly sensitive silicon microreactor for catalyst testing

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

Henriksen, Toke R.; Hansen, Ole; Department of Physics, Danish National Research Foundation's Center for Individual Nanoparticle Functionality

2009-12-15

A novel microfabricated chemical reactor for highly sensitive measurements of catalytic activity and surface kinetics is presented. The reactor is fabricated in a silicon chip and is intended for gas-phase reactions at pressures ranging from 0.1 to 5.0 bar. A high sensitivity is obtained by directing the entire gas flow through the catalyst bed to a mass spectrometer, thus ensuring that nearly all reaction products are present in the analyzed gas flow. Although the device can be employed for testing a wide range of catalysts, the primary aim of the design is to allow characterization of model catalysts which canmore » only be obtained in small quantities. Such measurements are of significant fundamental interest but are challenging because of the low surface areas involved. The relationship between the reaction zone gas flow and the pressure in the reaction zone is investigated experimentally. A corresponding theoretical model is presented, and the gas flow through an on-chip flow-limiting capillary is predicted to be in the intermediate regime. The experimental data for the gas flow are found to be in good agreement with the theoretical model. At typical experimental conditions, the total gas flow through the reaction zone is around 3x10{sup 14} molecules s{sup -1}, corresponding to a gas residence time in the reaction zone of about 11 s. To demonstrate the operation of the microreactor, CO oxidation on low-area platinum thin film circles is employed as a test reaction. Using temperature ramping, it is found that platinum catalysts with areas as small as 15 {mu}m{sup 2} are conveniently characterized with the device.« less

Reaction mechanism of WGS and PROX reactions catalyzed by Pt/oxide catalysts revealed by an FeO(111)/Pt(111) inverse model catalyst.

PubMed

Xu, Lingshun; Wu, Zongfang; Jin, Yuekang; Ma, Yunsheng; Huang, Weixin

2013-08-07

We have employed XPS and TDS to study the adsorption and surface reactions of H2O, CO and HCOOH on an FeO(111)/Pt(111) inverse model catalyst. The FeO(111)-Pt(111) interface of the FeO(111)/Pt(111) inverse model catalyst exposes coordination-unsaturated Fe(II) cations (Fe(II)CUS) and the Fe(II)CUS cations are capable of modifying the reactivity of neighbouring Pt sites. Water facilely dissociates on the Fe(II)CUS cations at the FeO(111)-Pt(111) interface to form hydroxyls that react to form both water and H2 upon heating. Hydroxyls on the Fe(II)CUS cations can react with CO(a) on the neighbouring Pt(111) sites to produce CO2 at low temperatures. Hydroxyls act as the co-catalyst in the CO oxidation by hydroxyls to CO2 (PROX reaction), while they act as one of the reactants in the CO oxidation by hydroxyls to CO2 and H2 (WGS reaction), and the recombinative reaction of hydroxyls to produce H2 is the rate-limiting step in the WGS reaction. A comparison of reaction behaviors between the interfacial CO(a) + OH reaction and the formate decomposition reaction suggest that formate is the likely surface intermediate of the CO(a) + OH reaction. These results provide some solid experimental evidence for the associative reaction mechanism of WGS and PROX reactions catalyzed by Pt/oxide catalysts.

Process for the synthesis of aliphatic alcohol-containing mixtures

DOEpatents

Greene, Marvin I.; Gelbein, Abraham P.

1984-01-01

A process for the synthesis of mixtures which include saturated aliphatic alcohols is disclosed. In the first step of the process, the first catalyst activation stage, a catalyst, which comprises the oxides of copper, zinc, aluminum, potassium and one or two additional metals selected from the group consisting of chromium, magnesium, cerium, cobalt, thorium and lanthanum, is partially activated. In this step, a reducing gas stream, which includes hydrogen and at least one inert gas, flows past the catalyst at a space velocity of up to 5,000 liters (STP) per hour, per kilogram of catalyst. The partially activated catalyst is then subjected to the second step of the process, second-stage catalyst activation. In this step, the catalyst is contacted by an activation gas stream comprising hydrogen and carbon monoxide present in a volume ratio of 0.5:1 and 4:1, respectively, at a temperature of 200.degree. to 450.degree. C. and a pressure of between 35 and 200 atmospheres. The activation gas flows at a space velocity of from 1,000 to 20,000 liters (STP) per hour, per kilogram of catalyst. Second-stage activation continues until the catalyst is contacted with at least 500,000 liters (STP) of activation gas per kilogram of catalyst. The fully activated catalyst, in the third step of the process, contacts a synthesis gas stream comprising hydrogen and carbon monoxide.

Process for the synthesis of aliphatic alcohol-containing mixtures

DOEpatents

Greene, M.I.; Gelbein, A.P.

1984-10-16

A process for the synthesis of mixtures which include saturated aliphatic alcohols is disclosed. In the first step of the process, the first catalyst activation stage, a catalyst, which comprises the oxides of copper, zinc, aluminum, potassium and one or two additional metals selected from the group consisting of chromium, magnesium, cerium, cobalt, thorium and lanthanum, is partially activated. In this step, a reducing gas stream, which includes hydrogen and at least one inert gas, flows past the catalyst at a space velocity of up to 5,000 liters (STP) per hour, per kilogram of catalyst. The partially activated catalyst is then subjected to the second step of the process, second-stage catalyst activation. In this step, the catalyst is contacted by an activation gas stream comprising hydrogen and carbon monoxide present in a volume ratio of 0.5:1 and 4:1, respectively, at a temperature of 200 to 450 C and a pressure of between 35 and 200 atmospheres. The activation gas flows at a space velocity of from 1,000 to 20,000 liters (STP) per hour, per kilogram of catalyst. Second-stage activation continues until the catalyst is contacted with at least 500,000 liters (STP) of activation gas per kilogram of catalyst. The fully activated catalyst, in the third step of the process, contacts a synthesis gas stream comprising hydrogen and carbon monoxide.

Computational and Physical Analysis of Catalytic Compounds

NASA Astrophysics Data System (ADS)

Wu, Richard; Sohn, Jung Jae; Kyung, Richard

2015-03-01

Nanoparticles exhibit unique physical and chemical properties depending on their geometrical properties. For this reason, synthesis of nanoparticles with controlled shape and size is important to use their unique properties. Catalyst supports are usually made of high-surface-area porous oxides or carbon nanomaterials. These support materials stabilize metal catalysts against sintering at high reaction temperatures. Many studies have demonstrated large enhancements of catalytic behavior due to the role of the oxide-metal interface. In this paper, the catalyzing ability of supported nano metal oxides, such as silicon oxide and titanium oxide compounds as catalysts have been analyzed using computational chemistry method. Computational programs such as Gamess and Chemcraft has been used in an effort to compute the efficiencies of catalytic compounds, and bonding energy changes during the optimization convergence. The result illustrates how the metal oxides stabilize and the steps that it takes. The graph of the energy computation step(N) versus energy(kcal/mol) curve shows that the energy of the titania converges faster at the 7th iteration calculation, whereas the silica converges at the 9th iteration calculation.

Compression Ratio and Catalyst Aging Effects on Aqueous Ethanol Ignition (Year 2) : Part 2 Catalyst Aging and Effects of Water on Ignition

DOT National Transportation Integrated Search

2009-09-01

A tubular plug-flow reactor under low Reynolds Numbers Re flow regimes, along with a 127 um diameter coiled platinum (Pt) wire, were used to study catalytic surface reactions of nonflammable, fuel-lean mixtures of propane, oxygen, and water vapor dil...

Temperature actuated automatic safety rod release

DOEpatents

Hutter, E.; Pardini, J.A.; Walker, D.E.

1984-03-13

A temperature-actuated apparatus is disclosed for releasably supporting a safety rod in a nuclear reactor, comprising a safety rod upper adapter having a retention means, a drive shaft which houses the upper adapter, and a bimetallic means supported within the drive shaft and having at least one ledge which engages a retention means of the safety rod upper adapter. A pre-determined increase in temperature causes the bimetallic means to deform so that the ledge disengages from the retention means, whereby the bimetallic means releases the safety rod into the core of the reactor.

Temperature actuated automatic safety rod release

DOEpatents

Hutter, Ernest; Pardini, John A.; Walker, David E.

1987-01-01

A temperature-actuated apparatus is disclosed for releasably supporting a safety rod in a nuclear reactor, comprising a safety rod upper adapter having a retention means, a drive shaft which houses the upper adapter, and a bimetallic means supported within the drive shaft and having at least one ledge which engages a retention means of the safety rod upper adapter. A pre-determined increase in temperature causes the bimetallic means to deform so that the ledge disengages from the retention means, whereby the bimetallic means releases the safety rod into the core of the reactor.

NH3-SCR denitration catalyst performance over vanadium-titanium with the addition of Ce and Sb.

PubMed

Xu, Chi; Liu, Jian; Zhao, Zhen; Yu, Fei; Cheng, Kai; Wei, Yuechang; Duan, Aijun; Jiang, Guiyuan

2015-05-01

Selective catalytic reduction technology using NH3 as a reducing agent (NH3-SCR) is an effective control method to remove nitrogen oxides. TiO2-supported vanadium oxide catalysts with different levels of Ce and Sb modification were prepared by an impregnation method and were characterized by X-ray diffractometer (XRD), Brunauer-Emmett-Teller (BET), Transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS), Raman and Hydrogen temperature-programmed reduction (H2-TPR). The catalytic activities of V5CexSby/TiO2 catalysts for denitration were investigated in a fixed bed flow microreactor. The results showed that cerium, vanadium and antimony oxide as the active components were well dispersed on TiO2, and the catalysts exhibited a large number of d-d electronic transitions, which were helpful to strengthen SCR reactivity. The V5CexSby/TiO2 catalysts exhibited a good low temperature NH3-SCR catalytic activity. In the temperature range of 210 to 400°C, the V5CexSby/TiO2 catalysts gave NO conversion rates above 90%. For the best V5Ce35Sb2/TiO2 catalyst, at a reaction temperature of 210°C, the NO conversion rate had already reached 90%. The catalysts had different catalytic activity with different Ce loadings. With the increase of Ce loading, the NO conversion rate also increased. Copyright © 2015. Published by Elsevier B.V.

Submergible torch for treating waste solutions and method thereof

DOEpatents

Mattus, Alfred J.

1995-01-01

A submergible torch for removing nitrate and/or nitrite ions from a waste solution containing nitrate and/or nitrite ions comprises: a torch tip, a fuel delivery mechanism, a fuel flow control mechanism, a catalyst, and a combustion chamber. The submergible torch is ignited to form a flame within the combustion chamber of the submergible torch. The torch is submerged in a waste solution containing nitrate and/or nitrite ions in such a manner that the flame is in contact with the waste solution and the catalyst and is maintained submerged for a period of time sufficient to decompose the nitrate and/or nitrite ions present in the waste solution.

Submergible torch for treating waste solutions and method thereof

DOEpatents

Mattus, Alfred J.

1994-01-01

A submergible torch for removing nitrate and/or nitrite ions from a waste solution containing nitrate and/or nitrite ions comprises: a torch tip, a fuel delivery mechanism, a fuel flow control mechanism, a catalyst, and a combustion chamber. The submergible torch is ignited to form a flame within the combustion chamber of the submergible torch. The torch is submerged in a waste solution containing nitrate and/or nitrite ions in such a manner that the flame is in contact with the waste solution and the catalyst and is maintained submerged for a period of time sufficient to decompose the nitrate and/or nitrite ions present in the waste solution.

A LabVIEW®-based software for the control of the AUTORAD platform: a fully automated multisequential flow injection analysis Lab-on-Valve (MSFIA-LOV) system for radiochemical analysis.

PubMed

Barbesi, Donato; Vicente Vilas, Víctor; Millet, Sylvain; Sandow, Miguel; Colle, Jean-Yves; Aldave de Las Heras, Laura

2017-01-01

A LabVIEW ® -based software for the control of the fully automated multi-sequential flow injection analysis Lab-on-Valve (MSFIA-LOV) platform AutoRAD performing radiochemical analysis is described. The analytical platform interfaces an Arduino ® -based device triggering multiple detectors providing a flexible and fit for purpose choice of detection systems. The different analytical devices are interfaced to the PC running LabVIEW ® VI software using USB and RS232 interfaces, both for sending commands and receiving confirmation or error responses. The AUTORAD platform has been successfully applied for the chemical separation and determination of Sr, an important fission product pertinent to nuclear waste.

Turbomachinery Clearance Control

NASA Technical Reports Server (NTRS)

Chupp, Raymond E.; Hendricks, Robert C.; Lattime, Scott B.; Steinetz, Bruce M.; Aksit, Mahmut F.

2007-01-01

Controlling interface clearances is the most cost effective method of enhancing turbomachinery performance. Seals control turbomachinery leakages, coolant flows and contribute to overall system rotordynamic stability. In many instances, sealing interfaces and coatings are sacrificial, like lubricants, giving up their integrity for the benefit of the component. They are subjected to abrasion, erosion, oxidation, incursive rubs, foreign object damage (FOD) and deposits as well as extremes in thermal, mechanical, aerodynamic and impact loadings. Tribological pairing of materials control how well and how long these interfaces will be effective in controlling flow. A variety of seal types and materials are required to satisfy turbomachinery sealing demands. These seals must be properly designed to maintain the interface clearances. In some cases, this will mean machining adjacent surfaces, yet in many other applications, coatings are employed for optimum performance. Many seals are coating composites fabricated on superstructures or substrates that are coated with sacrificial materials which can be refurbished either in situ or by removal, stripping, recoating and replacing until substrate life is exceeded. For blade and knife tip sealing an important class of materials known as abradables permit blade or knife rubbing without significant damage or wear to the rotating element while maintaining an effective sealing interface. Most such tip interfaces are passive, yet some, as for the high-pressure turbine (HPT) case or shroud, are actively controlled. This work presents an overview of turbomachinery sealing. Areas covered include: characteristics of gas and steam turbine sealing applications and environments, benefits of sealing, types of standard static and dynamics seals, advanced seal designs, as well as life and limitations issues.

Continuous flow room temperature reductive aqueous homo-coupling of aryl halides using supported Pd catalysts

PubMed Central

Feiz, Afsaneh; Bazgir, Ayoob; Balu, Alina M.; Luque, Rafael

2016-01-01

A convenient and environmentally friendly protocol for the preparation of biaryls at room temperature under continuous flow conditions is reported. A simple reductive homo-coupling Ullmann-type reaction was performed in an H-Cube mini using commercially available supported Pd catalysts under mild reaction conditions, with quantitative conversion to target products. Commercial Pd catalysts were found to be highly stable under the investigated reaction conditions, with a minimum Pd leaching into solution after several reaction runs (ca. 20 h on stream). PMID:27600989

Silica-Supported Catalyst for Enantioselective Arylation of Aldehydes under Batch and Continuous-Flow Conditions.

PubMed

Watanabe, Satoshi; Nakaya, Naoyuki; Akai, Junichiro; Kanaori, Kenji; Harada, Toshiro

2018-05-04

A silica-supported 3-aryl H 8 -BINOL-derived titanium catalyst exhibited high performance in the enantioselective arylation of aromatic aldehydes using Grignard and organolithium reagents not only under batch conditions but also under continuous-flow conditions. Even with a simple pipet reactor packed with the heterogeneous catalyst, the enantioselective production of chiral diarylmethanols could be achieved through a continuous introduction of aldehydes and mixed titanium reagents generated from the organometallic precursors. The pipet reactor could be used repeatedly in different reactions without appreciable deterioration of the activity.

Alignment control and atomically-scaled heteroepitaxial interface study of GaN nanowires.

PubMed

Liu, Qingyun; Liu, Baodan; Yang, Wenjin; Yang, Bing; Zhang, Xinglai; Labbé, Christophe; Portier, Xavier; An, Vladimir; Jiang, Xin

2017-04-20

Well-aligned GaN nanowires are promising candidates for building high-performance optoelectronic nanodevices. In this work, we demonstrate the epitaxial growth of well-aligned GaN nanowires on a [0001]-oriented sapphire substrate in a simple catalyst-assisted chemical vapor deposition process and their alignment control. It is found that the ammonia flux plays a key role in dominating the initial nucleation of GaN nanocrystals and their orientation. Typically, significant improvement of the GaN nanowire alignment can be realized at a low NH 3 flow rate. X-ray diffraction and cross-sectional scanning electron microscopy studies further verified the preferential orientation of GaN nanowires along the [0001] direction. The growth mechanism of GaN nanowire arrays is also well studied based on cross-sectional high-resolution transmission electron microscopy (HRTEM) characterization and it is observed that GaN nanowires have good epitaxial growth on the sapphire substrate following the crystallographic relationship between (0001) GaN ∥(0001) sapphire and (101[combining macron]0) GaN ∥(112[combining macron]0) sapphire . Most importantly, periodic misfit dislocations are also experimentally observed in the interface region due to the large lattice mismatch between the GaN nanowire and the sapphire substrate, and the formation of such dislocations will favor the release of structural strain in GaN nanowires. HRTEM analysis also finds the existence of "type I" stacking faults and voids inside the GaN nanowires. Optical investigation suggests that the GaN nanowire arrays have strong emission in the UV range, suggesting their crystalline nature and chemical purity. The achievement of aligned GaN nanowires will further promote the wide applications of GaN nanostructures toward diverse high-performance optoelectronic nanodevices including nano-LEDs, photovoltaic cells, photodetectors etc.

Interactions between bedforms, turbulence and pore flow

NASA Astrophysics Data System (ADS)

Blois, G.; Best, J.; Sambrook Smith, G.; Hardy, R. J.; Lead, J.

2010-12-01

A widespread occurrence of flow-form interaction in rivers is represented by subaqueous bedforms such as dunes. Many models have been proposed to explain how bedform generation and evolution are driven by turbulent flow structures that control the incipient motion of cohesionless sediments and later bedform development. However, most of these models have assumed such bedforms to be migrating over an impermeable bed, and that any surface-subsurface flow interaction is negligible. However, for some gravel-bed rivers the porosity can be high, up to 43%, which may result in significant flow both through the permeable bed (hyporheic flow) and across the surface-subsurface interface. The mass and momentum exchange occurring at the interface may have a strong impact on the structure of turbulent flow in the near-bed region. In the case of a dune, its topography induces a local pressure gradient that enhances flow across the interface. This results in a flow structure that may be radically different from that commonly proposed by past work. This paper presents results from a simplified laboratory model akin to a fine-grained bedform generated on top of a coarser sediment bed. Particle imaging velocimetry (PIV) measurements were conducted in order to characterise flow both over and underneath an idealised 2-dimensional dune (0.41 m long, 0.056 m high and having a leeside angle of 27°) overlaying a packed bed of uniform size spheres (D = 0.04 m diameter). Experiments were conducted in free surface flow conditions (Froude number = 0.1; Reynolds number = 25,000) for one bedform height: flow depth ratio (0.31). The flow above the dune was measured using a standard PIV technique while a novel endoscopic PIV (EPIV) system allowed collection of flow data within the pore spaces beneath the dune. The results show that topographically-induced subsurface flow significantly modifies the structure of flow in the leeside of the dune, resulting in a flow field that is radically different to traditional concepts of leeside flow. The pressure gradient across the bedform controls the direction and intensity of flow within the bed and across the interface. Specifically, the low pressure region induced by flow separation at the dune crest causes a pulsating jet flow from the bed into the free flow downstream of the dune. Fluid upwelling is particularly intense at the toe of the leeside and gradually decreases downstream. The interaction between the free-flow and hyporheic flow is significant; in the leeside, flow reattachment is entirely absent, and recirculation in the separation zone is replaced by a mechanism of asymmetric alternate vortex shedding. Hyporheic flow thus controls the dynamics of flow in the leeside and near-wake region. The paper discusses the implications of these results for the morphodynamics of coarse-sediment bedforms.

Highly functionalized biaryls via Suzuki-Miyaura cross-coupling catalyzed by Pd@MOF under batch and continuous flow regimes.

PubMed

Pascanu, Vlad; Hansen, Peter R; Bermejo Gómez, Antonio; Ayats, Carles; Platero-Prats, Ana E; Johansson, Magnus J; Pericàs, Miquel À; Martín-Matute, Belén

2015-01-01

A diverse set of more than 40 highly functionalized biaryls was synthesized successfully through the Suzuki-Miyaura cross-coupling reaction catalyzed by Pd nanoparticles supported in a functionalized mesoporous MOF (8 wt % Pd@MIL-101(Cr)-NH2 ). This could be achieved under some of the mildest conditions reported to date and a strong control over the leaching of metallic species could be maintained, despite the presence of diverse functional groups and/or several heteroatoms. Some of the targeted molecules are important intermediates in the synthesis of pharmaceuticals and we clearly exemplify the versatility of this catalytic system, which affords better yields than currently existing commercial procedures. Most importantly, Pd@MIL-101-NH2 was packed in a micro-flow reactor, which represents the first report of metallic nanoparticles supported on MOFs employed in flow chemistry for catalytic applications. A small library of 11 isolated compounds was created in a continuous experiment without replacing the catalyst, demonstrating the potential of the catalyst for large-scale applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Characteristics of back corona discharge in a honeycomb catalyst and its application for treatment of volatile organic compounds.

PubMed

Feng, Fada; Zheng, Yanyan; Shen, Xinjun; Zheng, Qinzhen; Dai, Shaolong; Zhang, Xuming; Huang, Yifan; Liu, Zhen; Yan, Keping

2015-06-02

The main technical challenges for the treatment of volatile organic compounds (VOCs) with plasma-assisted catalysis in industrial applications are large volume plasma generation under atmospheric pressure, byproduct control, and aerosol collection. To solve these problems, a back corona discharge (BCD) configuration has been designed to evenly generate nonthermal plasma in a honeycomb catalyst. Voltage-current curves, discharge images, and emission spectra have been used to characterize the plasma. Grade particle collection results and flow field visualization in the discharge zones show not only that the particles can be collected efficiently, but also that the pressure drop of the catalyst layer is relatively low. A three-stage plasma-assisted catalysis system, comprising a dielectric barrier discharge (DBD) stage, BCD stage, and catalyst stage, was built to evaluate toluene treatment performance by BCD. The ozone analysis results indicate that BCD enhances the ozone decomposition by collecting aerosols and protecting the Ag-Mn-O catalyst downstream from aerosol contamination. The GC and FTIR results show that BCD contributes to toluene removal, especially when the specific energy input is low, and the total removal efficiency reaches almost 100%. Furthermore, this removal results in the emission of fewer byproducts.

Inverse Catalysts for CO Oxidation: Enhanced Oxide–Metal Interactions in MgO/Au(111), CeO 2/Au(111), and TiO 2/Au(111)

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

Palomino, Robert M.; Gutiérrez, Ramón A.; Liu, Zongyuan

Au(111) does not bind CO and O 2 well. The deposition of small nanoparticles of MgO, CeO 2, and TiO 2 on Au(111) produces excellent catalysts for CO oxidation at room temperature. In an inverse oxide/metal configuration there is a strong enhancement of the oxide–metal interactions, and the inverse catalysts are more active than conventional Au/MgO(001), Au/CeO 2(111), and Au/TiO 2(110) catalysts. An identical trend was seen after comparing the CO oxidation activity of TiO2/Au and Au/TiO 2 powder catalysts. In the model systems, the activity increased following the sequence: MgO/Au(111) < CeO 2/Au(111) < TiO 2/Au(111). Ambient pressure X-raymore » photoelectron spectroscopy (AP-XPS) was used to elucidate the role of the titania–gold interface in inverse TiO 2/Au(111) model catalysts during CO oxidation. Stable surface intermediates such as CO(ads), CO 3 2–(ads), and OH(ads) were identified under reaction conditions. CO 3 2–(ads) and OH(ads) behaved as spectators. The concentration of CO(ad) initially increased and then decreased with increasing TiO 2 coverage, demonstrating a clear role of the Ti–Au interface and the size of the TiO 2 nanostructures in the catalytic process. Overall, our results show an enhancement in the strength of the oxide–metal interactions when working with inverse oxide/metal configurations, a phenomenon that can be utilized for the design of efficient catalysts useful for green and sustainable chemistry.« less

Inverse Catalysts for CO Oxidation: Enhanced Oxide–Metal Interactions in MgO/Au(111), CeO 2/Au(111), and TiO 2/Au(111)

DOE PAGES

Palomino, Robert M.; Gutiérrez, Ramón A.; Liu, Zongyuan; ...

2017-09-26

Au(111) does not bind CO and O 2 well. The deposition of small nanoparticles of MgO, CeO 2, and TiO 2 on Au(111) produces excellent catalysts for CO oxidation at room temperature. In an inverse oxide/metal configuration there is a strong enhancement of the oxide–metal interactions, and the inverse catalysts are more active than conventional Au/MgO(001), Au/CeO 2(111), and Au/TiO 2(110) catalysts. An identical trend was seen after comparing the CO oxidation activity of TiO2/Au and Au/TiO 2 powder catalysts. In the model systems, the activity increased following the sequence: MgO/Au(111) < CeO 2/Au(111) < TiO 2/Au(111). Ambient pressure X-raymore » photoelectron spectroscopy (AP-XPS) was used to elucidate the role of the titania–gold interface in inverse TiO 2/Au(111) model catalysts during CO oxidation. Stable surface intermediates such as CO(ads), CO 3 2–(ads), and OH(ads) were identified under reaction conditions. CO 3 2–(ads) and OH(ads) behaved as spectators. The concentration of CO(ad) initially increased and then decreased with increasing TiO 2 coverage, demonstrating a clear role of the Ti–Au interface and the size of the TiO 2 nanostructures in the catalytic process. Overall, our results show an enhancement in the strength of the oxide–metal interactions when working with inverse oxide/metal configurations, a phenomenon that can be utilized for the design of efficient catalysts useful for green and sustainable chemistry.« less

Metal catalysts for steam reforming of tar derived from the gasification of lignocellulosic biomass.

PubMed

Li, Dalin; Tamura, Masazumi; Nakagawa, Yoshinao; Tomishige, Keiichi

2015-02-01

Biomass gasification is one of the most important technologies for the conversion of biomass to electricity, fuels, and chemicals. The main obstacle preventing the commercial application of this technology is the presence of tar in the product gas. Catalytic reforming of tar appears a promising approach to remove tar and supported metal catalysts are among the most effective catalysts. Nevertheless, improvement of catalytic performances including activity, stability, resistance to coke deposition and aggregation of metal particles, as well as catalyst regenerability is greatly needed. This review focuses on the design and catalysis of supported metal catalysts for the removal of tar in the gasification of biomass. The recent development of metal catalysts including Rh, Ni, Co, and their alloys for steam reforming of biomass tar and tar model compounds is introduced. The role of metal species, support materials, promoters, and their interfaces is described. Copyright © 2014 Elsevier Ltd. All rights reserved.

Scaling-Relation-Based Analysis of Bifunctional Catalysis: The Case for Homogeneous Bimetallic Alloys

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

Andersen, Mie; Medford, Andrew J.; Norskov, Jens K.

Here, we present a generic analysis of the implications of energetic scaling relations on the possibilities for bifunctional gains at homogeneous bimetallic alloy catalysts. Such catalysts exhibit a large number of interface sites, where second-order reaction steps can involve intermediates adsorbed at different active sites. Using different types of model reaction schemes, we show that such site-coupling reaction steps can provide bifunctional gains that allow for a bimetallic catalyst composed of two individually poor catalyst materials to approach the activity of the optimal monomaterial catalyst. However, bifunctional gains cannot result in activities higher than the activity peak of the monomaterialmore » volcano curve as long as both sites obey similar scaling relations, as is generally the case for bimetallic catalysts. These scaling-relation-imposed limitations could be overcome by combining different classes of materials such as metals and oxides.« less

Scaling-Relation-Based Analysis of Bifunctional Catalysis: The Case for Homogeneous Bimetallic Alloys

DOE PAGES

Andersen, Mie; Medford, Andrew J.; Norskov, Jens K.; ...

2017-04-14

Here, we present a generic analysis of the implications of energetic scaling relations on the possibilities for bifunctional gains at homogeneous bimetallic alloy catalysts. Such catalysts exhibit a large number of interface sites, where second-order reaction steps can involve intermediates adsorbed at different active sites. Using different types of model reaction schemes, we show that such site-coupling reaction steps can provide bifunctional gains that allow for a bimetallic catalyst composed of two individually poor catalyst materials to approach the activity of the optimal monomaterial catalyst. However, bifunctional gains cannot result in activities higher than the activity peak of the monomaterialmore » volcano curve as long as both sites obey similar scaling relations, as is generally the case for bimetallic catalysts. These scaling-relation-imposed limitations could be overcome by combining different classes of materials such as metals and oxides.« less

Evaluation of Commercial Off-the-Shelf Sorbents and Catalysts for Control of Ammonia and Carbon Monoxide

NASA Technical Reports Server (NTRS)

Luna, Bernadette; Somi, George; Winchester, J. Parker; Grose, Jeffrey; Mulloth, Lila; Perry, Jay L.

2010-01-01

Designers of future space vehicles envision simplifying the Atmosphere Revitalization (AR) system by combining the functions of trace contaminant (TC) control and carbon dioxide removal into one swing-bed system. Flow rates and bed sizes of the TC and CO2 systems have historically been very different. There is uncertainty about the ability of trace contaminant sorbents to adsorb adequately in high-flow or short bed length configurations, and to desorb adequately during short vacuum exposures. There is also concern about ambient ammonia levels in the absence of a condensing heat exchanger. In addition, new materials and formulations have become commercially available, formulations never evaluated by NASA for purposes of trace contaminant control. The optimal air revitalization system for future missions may incorporate a swing-bed system for carbon dioxide (CO2) and partial trace contaminant control, with a reduced-size, low-power, targeted trace contaminant system supplying the remaining contaminant removal capability. This paper describes the results of a comparative experimental investigation into materials for trace contaminant control that might be part of such a system. Ammonia sorbents and low temperature carbon monoxide (CO) oxidation catalysts are the foci. The data will be useful to designers of AR systems for future flexible path missions. This is a continuation of work presented in a prior year, with extended test results.

Evaluation of Commercial Off-the-Shelf Sorbents and Catalysts for Control of Ammonia and Carbon Monoxide

NASA Technical Reports Server (NTRS)

Luna, Bernadette; Somi, George; Winchester, J. Parker; Grose, Jeffrey; Mulloth, Lila; Perry, Jay L.

2013-01-01

Designers of future space vehicles envision simplifying the Atmosphere Revitalization (AR) system by combining the functions of trace contaminant (TC) control and carbon dioxide removal into one swing-bed system. Flow rates and bed sizes of the TC and CO2 systems have historically been very different. There is uncertainty about the ability of trace contaminant sorbents to adsorb adequately in high-flow or short bed length configurations, and to desorb adequately during short vacuum exposures. There is also concern about ambient ammonia levels in the absence of a condensing heat exchanger. In addition, new materials and formulations have become commercially available, formulations never evaluated by NASA for purposes of trace contaminant control. The optimal air revitalization system for future missions may incorporate a swing-bed system for carbon dioxide (CO2) and partial trace contaminant control, with a reduced-size, low-power, targeted trace contaminant system supplying the remaining contaminant removal capability. This paper describes the results of a comparative experimental investigation into materials for trace contaminant control that might be part of such a system. Ammonia sorbents and low temperature carbon monoxide (CO) oxidation catalysts are the foci. The data will be useful to designers of AR systems for future flexible path missions. This is a continuation of work presented in a prior year, with extended test results.

ZnO/perovskite core–shell nanorod array based monolithic catalysts with enhanced propane oxidation and material utilization efficiency at low temperature

DOE PAGES

Wang, Sibo; Ren, Zheng; Song, Wenqiao; ...

2015-04-24

Here, a hydrothermal strategy combined with colloidal deposition synthesis was successfully used to grow ZnO/perovskite (LaBO 3, B=Mn, Co, Ni) core-shell nanorod arrays within three dimensional (3-D) honeycomb cordierite substrates. A facile sonication assisted colloidal wash coating process is able to coat a uniformly dispersed perovskite nanoparticles onto the large scale ZnO nanorod arrays rooted on the channel surfaces of the 3D cordierite substrate achieved by hydrothermal synthesis. Compared to traditional wash-coated perovskite catalysts, an enhanced catalytic performance was observed for propane oxidation with 25°C lower light-off temperature than wash-coated perovskite catalyst of similar LaMnO 3 loading (4.3mg). Temperature programmedmore » reduction and desorption under H 2 and O 2 atmosphere, respectively, were used to study the reducibility and oxygen activity of these core-shell nanorod arrays based monolithic catalysts, revealing a catalytic activity sequence of LaCoO 3>LaMnO 3>La 2NiO 4 at the initial stage of catalytic reaction. The good dispersion and size control in La-based perovskite nanoparticles and their interfaces to ZnO nanorod arrays support may contribute to the enhancement of catalytic performance. Lastly, this work may provide a new type of Pt-group metals (PGM) free catalysts with improved catalytic performance for hydrocarbon oxidations at low temperatures.« less

Thermal Catalytic Oxidation of Airborne Contaminants by a Reactor Using Ultra-Short Channel Length, Monolithic Catalyst Substrates

NASA Technical Reports Server (NTRS)

Perry, J. L.; Tomes, K. M.; Tatara, J. D.

2005-01-01

Contaminated air, whether in a crewed spacecraft cabin or terrestrial work and living spaces, is a pervasive problem affecting human health, performance, and well being. The need for highly effective, economical air quality processes spans a wide range of terrestrial and space flight applications. Typically, air quality control processes rely on absorption-based processes. Most industrial packed-bed adsorption processes use activated carbon. Once saturated, the carbon is either dumped or regenerated. In either case, the dumped carbon and concentrated waste streams constitute a hazardous waste that must be handled safely while minimizing environmental impact. Thermal catalytic oxidation processes designed to address waste handling issues are moving to the forefront of cleaner air quality control and process gas decontamination processes. Careful consideration in designing the catalyst substrate and reactor can lead to more complete contaminant destruction and poisoning resistance. Maintenance improvements leading to reduced waste handling and process downtime can also be realized. Performance of a prototype thermal catalytic reaction based on ultra-short waste channel, monolith catalyst substrate design, under a variety of process flow and contaminant loading conditions, is discussed.

Ledge-type Co/L1{sub 0}-FePt exchange-coupled composites

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

Speliotis, Th.; Giannopoulos, G.; Niarchos, D.

2016-06-21

FePt-based exchange-coupled composites consisting of a magnetically hard L1{sub 0}-FePt phase exchange-coupled with a soft ferromagnetic material are promising candidates for future ultra-high density (>1 Tbit/in{sup 2}) perpendicular magnetic recording media, also being of interest for other applications including spin torque oscillators and micro-electro-mechanical systems, among others. In this paper, the effect of the thickness of a soft Co layer (3 < th{sub Co} < 20 nm) on the magnetic behavior of ledge-type fcc(100)-Co/L1{sub 0}(001)-FePt composites deposited on an MgO (100) substrate is systematically studied by combining morpho-structural analyses and angular magnetization measurements. Starting from a film consisting of isolated L1{submore » 0}(001)–FePt islands, the ledge-type structure was obtained by depositing a Co layer that either covered the FePt islands or filled-up the inter-island region, gradually forming a continuous layer with increasing Co thickness. A perpendicular anisotropy was maintained up to th{sub Co} ∼ 9.5 nm and a significant reduction in the coercivity (about 50% for th{sub Co} ∼ 3 nm) with the increase in th{sub Co} was observed, indicating that, by coupling hard FePt and soft Co phases in a ledge-type configuration, the writability can be greatly improved. Recoil loops' measurements confirmed the exchange-coupled behavior, reinforcing a potential interest in these systems for future magnetic recording media.« less

Carbon Dioxide Methanation for Human Exploration of Mars: A Look at Catalyst Longevity and Activity Using Supported Ruthenium

NASA Technical Reports Server (NTRS)

Petersen, Elspeth M.; Meier, Anne J.; Tessonnier, Jean-Philippe

2018-01-01

Overarching Purpose: To design a carbon dioxide methanation/Sabatier reaction catalyst able to withstand variable conditions including fluctuations in bed temperature and feed flow rates for 480 days of remote operation to produce seven tons of methane. Current Study Purpose: Examine supported Ruthenium as a carbon dioxide methanation catalyst to determine the effects support properties have on the active phase by studying activity and selectivity. Objective: The remote operation of the Mars ISRU (In Situ Resources Utilization) lander to produce rocket fuel prior to crew arrival on the planet to power an ascent vehicle. Constraints: Long-term operation (480 days); Variable conditions: Feed gas flow rates, Feed gas flow ratios, Reactor bed temperature.

Selective Catalytic Combustion Sensors for Reactive Organic Analysis

NASA Technical Reports Server (NTRS)

Innes, W. B.

1971-01-01

Sensors involving a vanadia-alumina catalyst bed-thermocouple assembly satisfy requirements for simple, reproducible and rapid continuous analysis or reactive organics. Responses generally increase with temperature to 400 C and increase to a maximum with flow rate/catalyst volume. Selectivity decreases with temperature. Response time decreases with flow rate and increases with catalyst volume. At chosen optimum conditions calculated response which is additive and linear agrees better with photochemical reactivity than other methods for various automotive sources, and response to vehicle exhaust is insensitive to flow rate. Application to measurement of total reactive organics in vehicle exhaust as well as for gas chromatography detection illustrate utility. The approach appears generally applicable to high thermal effect reactions involving first order kinetics.

Continuous Heterogeneous Photocatalysis in Serial Micro-Batch Reactors.

PubMed

Pieber, Bartholomäus; Shalom, Menny; Antonietti, Markus; Seeberger, Peter H; Gilmore, Kerry

2018-01-29

Solid reagents, leaching catalysts, and heterogeneous photocatalysts are commonly employed in batch processes but are ill-suited for continuous-flow chemistry. Heterogeneous catalysts for thermal reactions are typically used in packed-bed reactors, which cannot be penetrated by light and thus are not suitable for photocatalytic reactions involving solids. We demonstrate that serial micro-batch reactors (SMBRs) allow for the continuous utilization of solid materials together with liquids and gases in flow. This technology was utilized to develop selective and efficient fluorination reactions using a modified graphitic carbon nitride heterogeneous catalyst instead of costly homogeneous metal polypyridyl complexes. The merger of this inexpensive, recyclable catalyst and the SMBR approach enables sustainable and scalable photocatalysis. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Environmental Technology Verification: Test Report of Mobile Source Emission Control Devices--Johnson Matthey PCRT2 1000, Version 2, Filter + Diesel Oxidation Catalyst

EPA Science Inventory

The Johnson Matthey PCRT2 1000, v.2 system is a partial continuously regenerating technology (PCRT) system that consists of a flow-through partial filter combined with a DOC. The system is designed for low temperature exhaust resulting from intermittent loads from medium and heav...

Electrochemical performance and durability of carbon supported Pt catalyst in contact with aqueous and polymeric proton conductors.

PubMed

Andersen, Shuang Ma; Skou, Eivind

2014-10-08

Significant differences in catalyst performance and durability are often observed between the use of a liquid electrolyte (e.g., sulfuric acid), and a solid polymer electrolyte (e.g., Nafion). To understand this phenomenon, we studied the electrochemical behavior of a commercially available carbon supported platinum catalyst in four different electrode structures: catalyst powder (CP), catalyst ionomer electrode (CIE), half membrane electrode assembly (HMEA), and full membrane electrode assembly (FMEA) in both ex situ and in situ experiments under a simulated start/stop cycle. We found that the catalyst performance and stability are very much influenced by the presence of the Nafion ionomers. The proton conducting phase provided by the ionomer and the self-assembled electrode structure render the catalysts a higher utilization and better stability. This is probably due to an enhanced dispersion, an improved proton-catalyst interface, the restriction of catalyst particle aggregation, and the improved stability of the ionomer phase especially after the lamination. Therefore, an innovative electrode HMEA design for ex-situ catalyst characterization is proposed. The electrode structure is identical to the one used in a real fuel cell, where the protons transport takes place solely through solid state proton conducting phase.

Heterogeneous Pd catalysts as emulsifiers in Pickering emulsions for integrated multistep synthesis in flow chemistry.

PubMed

Hiebler, Katharina; Lichtenegger, Georg J; Maier, Manuel C; Park, Eun Sung; Gonzales-Groom, Renie; Binks, Bernard P; Gruber-Woelfler, Heidrun

2018-01-01

Within the "compartmentalised smart factory" approach of the ONE-FLOW project the implementation of different catalysts in "compartments" provided by Pickering emulsions and their application in continuous flow is targeted. We present here the development of heterogeneous Pd catalysts that are ready to be used in combination with biocatalysts for catalytic cascade synthesis of active pharmaceutical ingredients (APIs). In particular, we focus on the application of the catalytic systems for Suzuki-Miyaura cross-coupling reactions, which is the key step in the synthesis of the targeted APIs valsartan and sacubitril. An immobilised enzyme will accomplish the final product formation via hydrolysis. In order to create a large interfacial area for the catalytic reactions and to keep the reagents separated until required, the catalyst particles are used to stabilise Pickering emulsions of oil and water. A set of Ce-Sn-Pd oxides with the molecular formula Ce 0.99- x Sn x Pd 0.01 O 2-δ ( x = 0-0.99) has been prepared utilising a simple single-step solution combustion method. The high applicability of the catalysts for different functional groups and their minimal leaching behaviour is demonstrated with various Suzuki-Miyaura cross-coupling reactions in batch as well as in continuous flow employing the so-called "plug & play reactor". Finally, we demonstrate the use of these particles as the sole emulsifier of oil-water emulsions for a range of oils.

Electronic and local atomistic structure of MgSiO3 glass under pressure: a study of X-ray Raman scattering at the silicon and magnesium L-edges

NASA Astrophysics Data System (ADS)

Fukui, Hiroshi; Hiraoka, Nozomu

2018-02-01

We applied X-ray Raman scattering technique to MgSiO3 glass, a precursor to magnesium silicate melts, with respect to magnesium and silicon under high-pressure conditions as well as some polycrystalline phases of MgSiO3 at ambient conditions. We also performed ab initio calculations to interpret the X-ray Raman spectra. Experimentally obtained silicon L-edge spectra indicate that the local environment around silicon started changing at pressure above 10 GPa, where the electronic structure of oxygen is known to change. In contrast, the shape of the magnesium L-edge spectrum changed below 10 GPa. This indicates that the magnesium sites in MgSiO3 glass first distort and that the local structure around magnesium shows a wide variation under pressure. The framework structure consisting of silicon and oxygen changed above 10 GPa, where the coordination number of silicon was more than four. Our results imply that 6-oxygen-coordinated silicon was formed above 20 GPa.

Soft x-ray absorption spectroscopy of metalloproteins and high-valent metal-complexes at room temperature using free-electron lasers

PubMed Central

Kubin, Markus; Kern, Jan; Gul, Sheraz; Kroll, Thomas; Chatterjee, Ruchira; Löchel, Heike; Fuller, Franklin D.; Sierra, Raymond G.; Quevedo, Wilson; Weniger, Christian; Rehanek, Jens; Firsov, Anatoly; Laksmono, Hartawan; Weninger, Clemens; Alonso-Mori, Roberto; Nordlund, Dennis L.; Lassalle-Kaiser, Benedikt; Glownia, James M.; Krzywinski, Jacek; Moeller, Stefan; Turner, Joshua J.; Minitti, Michael P.; Dakovski, Georgi L.; Koroidov, Sergey; Kawde, Anurag; Kanady, Jacob S.; Tsui, Emily Y.; Suseno, Sandy; Han, Zhiji; Hill, Ethan; Taguchi, Taketo; Borovik, Andrew S.; Agapie, Theodor; Messinger, Johannes; Erko, Alexei; Föhlisch, Alexander; Bergmann, Uwe; Mitzner, Rolf; Yachandra, Vittal K.; Yano, Junko; Wernet, Philippe

2017-01-01

X-ray absorption spectroscopy at the L-edge of 3d transition metals provides unique information on the local metal charge and spin states by directly probing 3d-derived molecular orbitals through 2p-3d transitions. However, this soft x-ray technique has been rarely used at synchrotron facilities for mechanistic studies of metalloenzymes due to the difficulties of x-ray-induced sample damage and strong background signals from light elements that can dominate the low metal signal. Here, we combine femtosecond soft x-ray pulses from a free-electron laser with a novel x-ray fluorescence-yield spectrometer to overcome these difficulties. We present L-edge absorption spectra of inorganic high-valent Mn complexes (Mn ∼ 6–15 mmol/l) with no visible effects of radiation damage. We also present the first L-edge absorption spectra of the oxygen evolving complex (Mn4CaO5) in Photosystem II (Mn < 1 mmol/l) at room temperature, measured under similar conditions. Our approach opens new ways to study metalloenzymes under functional conditions. PMID:28944255

Soft x-ray absorption spectroscopy of metalloproteins and high-valent metal-complexes at room temperature using free-electron lasers

DOE PAGES

Kubin, Markus; Kern, Jan; Gul, Sheraz; ...

2017-09-01

X-ray absorption spectroscopy at the L-edge of 3d transition metals provides unique information on the local metal charge and spin states by directly probing 3d-derived molecular orbitals through 2p-3d transitions. But, this soft x-ray technique has been rarely used at synchrotron facilities for mechanistic studies of metalloenzymes due to the difficulties of x-ray-induced sample damage and strong background signals from light elements that can dominate the low metal signal. Here, we combine femtosecond soft x-ray pulses from a free-electron laser with a novel x-ray fluorescence-yield spectrometer to overcome these difficulties. We present L-edge absorption spectra of inorganic high-valent Mn complexesmore » (Mn ~ 6-15 mmol/l) with no visible effects of radiation damage. We then present the first L-edge absorption spectra of the oxygen evolving complex (Mn 4 CaO 5 ) in Photosystem II (Mn < 1 mmol/l) at room temperature, measured under similar conditions. Our approach opens new ways to study metalloenzymes under functional conditions.« less

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

PubMed

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

2017-11-22

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

Boundary-layer-ingesting inlet flow control system

NASA Technical Reports Server (NTRS)

Owens, Lewis R. (Inventor); Allan, Brian G. (Inventor)

2010-01-01

A system for reducing distortion at the aerodynamic interface plane of a boundary-layer-ingesting inlet using a combination of active and passive flow control devices is disclosed. Active flow control jets and vortex generating vanes are used in combination to reduce distortion across a range of inlet operating conditions. Together, the vortex generating vanes can reduce most of the inlet distortion and the active flow control jets can be used at a significantly reduced control jet mass flow rate to make sure the inlet distortion stays low as the inlet mass flow rate varies. Overall inlet distortion, measured and described as average SAE circumferential distortion descriptor, was maintained at a value of 0.02 or less. Advantageous arrangements and orientations of the active flow control jets and the vortex generating vanes were developed using computational fluid dynamics simulations and wind tunnel experimentations.

Anh To | NREL

Science.gov Websites

pyrolysis vapors Catalytic depolymerization of biomass Process scale-up for catalyst synthesis and testing continuous flow reactors (gas & liquid phases) Catalyst synthesis: zeolites, supported metals, and

Enhancing CO2 Electroreduction with the Metal-Oxide Interface.

PubMed

Gao, Dunfeng; Zhang, Yi; Zhou, Zhiwen; Cai, Fan; Zhao, Xinfei; Huang, Wugen; Li, Yangsheng; Zhu, Junfa; Liu, Ping; Yang, Fan; Wang, Guoxiong; Bao, Xinhe

2017-04-26

The electrochemical CO 2 reduction reaction (CO 2 RR) typically uses transition metals as the catalysts. To improve the efficiency, tremendous efforts have been dedicated to tuning the morphology, size, and structure of metal catalysts and employing electrolytes that enhance the adsorption of CO 2 . We report here a strategy to enhance CO 2 RR by constructing the metal-oxide interface. We demonstrate that Au-CeO x shows much higher activity and Faradaic efficiency than Au or CeO x alone for CO 2 RR. In situ scanning tunneling microscopy and synchrotron-radiation photoemission spectroscopy show that the Au-CeO x interface is dominant in enhancing CO 2 adsorption and activation, which can be further promoted by the presence of hydroxyl groups. Density functional theory calculations indicate that the Au-CeO x interface is the active site for CO 2 activation and the reduction to CO, where the synergy between Au and CeO x promotes the stability of key carboxyl intermediate (*COOH) and thus facilitates CO 2 RR. Similar interface-enhanced CO 2 RR is further observed on Ag-CeO x , demonstrating the generality of the strategy for enhancing CO 2 RR.

Enhancing CO 2 electroreduction with the metal–oxide interface

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

Gao, Dunfeng; Zhang, Yi; Zhou, Zhiwen

2017-04-09

Here, the electrochemical CO 2 reduction reaction (CO 2RR) typically uses transition metals as the catalysts. To improve the efficiency, tremendous efforts have been dedicated to tuning the morphology, size, and structure of metal catalysts and employing electrolytes that enhance the adsorption of CO 2. We report here a strategy to enhance CO 2RR by constructing the metal–oxide interface. We demonstrate that Au–CeO x shows much higher activity and Faradaic efficiency than Au or CeO x alone for CO 2RR. In situ scanning tunneling microscopy and synchrotron-radiation photoemission spectroscopy show that the Au–CeO x interface is dominant in enhancing COmore » 2 adsorption and activation, which can be further promoted by the presence of hydroxyl groups. Density functional theory calculations indicate that the Au–CeO x interface is the active site for CO 2 activation and the reduction to CO, where the synergy between Au and CeO x promotes the stability of key carboxyl intermediate (*COOH) and thus facilitates CO 2RR. Similar interface-enhanced CO 2RR is further observed on Ag–CeO x, demonstrating the generality of the strategy for enhancing CO 2RR.« less

Test Program for Assessing Vulnerability of Industrial Equipment to Nuclear Air Blast.

DTIC Science & Technology

1983-10-01

PROJECT. TASK 4Scientific Servic, Inc. AREA & WORK UNIT NUMBERS 517 East Bayshore Work Unit 1124F Redwood City, CA 94063___ __________ 11. CONTROLLING ...vulnerability, but perhaps less expensive, to be selected and substituted, with an eye to cost control . 5. MODELING AND SCALING CONSIDERATIONS Reiterating...behavior and properties of the test items and Interfaces that control behavior (e4g., test objects/flow field, test objects/interfacing surface of

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.

Cooling by Para-to-Ortho-Hydrogen Conversion

NASA Technical Reports Server (NTRS)

Sherman, A.; Nast, T.

1983-01-01

Catalyst speeds conversion, increasing capacity of solid hydrogen cooling system. In radial-flow catalytic converter, para-hydrogen is converted to equilibrium mixture of para-hydrogen and ortho-hydrogen as it passes through porous cylinder of catalyst. Addition of catalyst increases capacity of hydrogen sublimation cooling systems for radiation detectors.

Dynamic fluid connectivity during steady-state multiphase flow in a sandstone.

PubMed

Reynolds, Catriona A; Menke, Hannah; Andrew, Matthew; Blunt, Martin J; Krevor, Samuel

2017-08-01

The current conceptual picture of steady-state multiphase Darcy flow in porous media is that the fluid phases organize into separate flow pathways with stable interfaces. Here we demonstrate a previously unobserved type of steady-state flow behavior, which we term "dynamic connectivity," using fast pore-scale X-ray imaging. We image the flow of N 2 and brine through a permeable sandstone at subsurface reservoir conditions, and low capillary numbers, and at constant fluid saturation. At any instant, the network of pores filled with the nonwetting phase is not necessarily connected. Flow occurs along pathways that periodically reconnect, like cars controlled by traffic lights. This behavior is consistent with an energy balance, where some of the energy of the injected fluids is sporadically converted to create new interfaces.

A Numerical Investigation of the Effect of Thermoelectromagnetic Convection (TEMC) on the Bridgman Growth of Ge(1-x)Si(x)

NASA Technical Reports Server (NTRS)

Yesilyurt, Serhat; Vujisic, Ljubomir; Motakef, Shariar; Szofran, F. R.; Volz, Martin P.

1998-01-01

Thermoelectric currents at the growth interface of GeSi during Bridgman growth are shown to promote convection when a low intensity axial magnetic field is applied. TEMC, typically, is characterized by a meridional flow driven by the rotation of the fluid; meridional convection alters composition of the melt, and shape of the growth interface substantially. TEMC effect is more important in micro-gravity environment than the terrestrial one, and can be used to control convection during the growth of GeSi. In this work, coupled thermo-solutal flow equations (energy, scalar transport, momentum and mass) are solved in tandem with Maxwell's equations to compute the thermo-solutat flow field, electric currents, and the growth-interface shape.

Performance of a High-Fidelity 4kW-Class Engineering Model PPU and Integration with HiVHAc System

NASA Technical Reports Server (NTRS)

Pinero, Luis R.; Kamhawi, Hani; Shilo, Vladislav

2016-01-01

The High Voltage Hall Accelerator (HiVHAc) propulsion system consists of a thruster,power processing unit (PPU), and propellant feed system. An engineering model PPU was developed by Colorado Power Electronics, Inc. funded by NASA's Small Business Innovative Research Program. This PPU uses an innovative 3-phase resonant converter to deliver 4 kW of discharge power over a wide range of input and output voltage conditions.The PPU includes a digital control interface unit that automatically controls the PPU and a xenon flow control module (XFCM). It interfaces with a control computer to receive high level commands and relay telemetry through a MIL-STD-1553B interface. The EM PPU was thoroughly tested at GRC for functionality and performance at temperature extremes and demonstrated total efficiencies a high as 95 percent. It was integrated with the HiVHAc thruster and the XFCM to demonstrate closed-loop control of discharge current with anode flow. Initiation of the main discharge and power throttling were also successfully demonstrated and discharge oscillations were characterized.

Performance of a High-Fidelity 4kW-Class Engineering Model PPU and Integration with HiVHAc System

NASA Technical Reports Server (NTRS)

Pinero, Luis R.; Kamhawi, Hani; Shilo, Vlad

2016-01-01

The High Voltage Hall Accelerator (HiVHAc) propulsion system consists of a thruster, power processing unit (PPU), and propellant feed system. An engineering model PPU was developed by Colorado Power Electronics, Inc. funded by NASA's Small Business Innovative Research Program. This PPU uses an innovative 3-phase resonant converter to deliver 4 kW of discharge power over a wide range of input and output voltage conditions. The PPU includes a digital control interface unit that automatically controls the PPU and a xenon flow control module (XFCM). It interfaces with a control computer to receive highlevel commands and relay telemetry through a MIL-STD-1553B interface. The EM PPU was thoroughly tested at GRC for functionality and performance at temperature limits and demonstrated total efficiencies a high as 95 percent. Integrated testing of the unit was performed with the HiVHAc thruster and the XFCM to demonstrate closed-loop control of discharge current with anode flow. Initiation of the main discharge and power throttling were also successfully demonstrated and discharge oscillations were characterized.

Hierarchical Heterogeneity at the CeO x –TiO 2 Interface: Electronic and Geometric Structural Influence on the Photocatalytic Activity of Oxide on Oxide Nanostructures

DOE PAGES

Luo, Si; Nguyen-Phan, Thuy-Duong; Johnston-Peck, Aaron C.; ...

2015-01-13

Mixed oxide interfaces are critical for delivering active components of demanding catalytic processes such as the photo-catalytic splitting of water. We have studied CeO xTiO₂ catalysts with low ceria loadings of 1 wt%, 3 wt% and 6 wt% that were prepared with wet impregnation methods to favor a strong interaction between CeO x and TiO₂. In these materials the interfaces between CeO x-TiO₂ have been sequentially loaded (1%, 3% and 6%), with and without Pt (0.5 wt%). The structure and properties of the catalysts were characterized using several X-ray and electron based techniques including XRD, XPS, UPS, NEXAFS, UV-Vis andmore » HR-STEM/STEM-EELS, to unravel the local morphology, bulk structure, surface states and electronic structure. The combination of all these techniques allow us to analyze in a systematic way the complete structural and electronic properties that prevail at the CeO x-TiO₂ interface. Fluorite structured nano crystallites of ceria on anatase-structured titania were identified by both XRD and NEXAFS. A sequential increasing of the CeO x loading led to the formation of clusters, then plates and finally nano particles in a hierarchical manner on the TiO₂ support. The electronic structures of these catalysts indicate that the interaction between TiO₂ and CeO₂ is closely related to the local morphology of nanostructured CeO₂. Ce³⁺ cations were detected at the surface of CeO₂ and at the interface of the two oxides. In addition, the titania is perturbed by the interaction with ceria and also with Pt. The photocatalytic activity for the splitting of H₂O using UV light was measured for these materials and correlated with our understanding of the electronic and structural properties. Optimal catalytic performance and photo response results were found for the 1 wt% CeO x-TiO₂ catalyst where low dimensional geometry of the ceria provided ideal electronic and geometrical properties. The structural and electronic properties of the interface were critical for the photocatalytic performance of this mixed-oxide nanocatalyst system.« less

Autothermal and partial oxidation reformer-based fuel processor, method for improving catalyst function in autothermal and partial oxidation reformer-based processors

DOEpatents

Ahmed, Shabbir; Papadias, Dionissios D.; Lee, Sheldon H. D.; Ahluwalia, Rajesh K.

2013-01-08

The invention provides a fuel processor comprising a linear flow structure having an upstream portion and a downstream portion; a first catalyst supported at the upstream portion; and a second catalyst supported at the downstream portion, wherein the first catalyst is in fluid communication with the second catalyst. Also provided is a method for reforming fuel, the method comprising contacting the fuel to an oxidation catalyst so as to partially oxidize the fuel and generate heat; warming incoming fuel with the heat while simultaneously warming a reforming catalyst with the heat; and reacting the partially oxidized fuel with steam using the reforming catalyst.

Hydrogenation of CO 2 to methanol on CeO x/Cu(111) and ZnO/Cu(111) catalysts: Role of the metal-oxide interface and importance of Ce 3+ sites

DOE PAGES

Senanayake, Sanjaya D.; Ramirez, Pedro J.; Waluyo, Iradwikanari; ...

2016-01-06

The role of the interface between a metal and oxide (CeO x–Cu and ZnO–Cu) is critical to the production of methanol through the hydrogenation of CO 2 (CO 2 + 3H 2 → CH 3OH + H 2O). The deposition of nanoparticles of CeO x or ZnO on Cu(111), θ oxi < 0.3 monolayer, produces highly active catalysts for methanol synthesis. The catalytic activity of these systems increases in the sequence: Cu(111) < ZnO/Cu(111) < CeO x/Cu(111). The apparent activation energy for the CO 2 → CH 3OH conversion decreases from 25 kcal/mol on Cu(111) to 16 kcal/mol on ZnO/Cu(111)more » and 13 kcal/mol on CeO x/Cu(111). The surface chemistry of the highly active CeO x–Cu(111) interface was investigated using ambient pressure X-ray photoemission spectroscopy (AP-XPS) and infrared reflection absorption spectroscopy (AP-IRRAS). Both techniques point to the formation of formates (HCOO –) and carboxylates (CO 2 δ–) during the reaction. Our results show an active state of the catalyst rich in Ce 3+ sites which stabilize a CO 2 δ– species that is an essential intermediate for the production of methanol. Furthermore, the inverse oxide/metal configuration favors strong metal–oxide interactions and makes possible reaction channels not seen in conventional metal/oxide catalysts.« less

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

NASA Astrophysics Data System (ADS)

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

2015-08-01

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

Co and Fe-catalysts supported on sepiolite: effects of preparation conditions on their catalytic behaviors in high temperature gas flow treatment of dye.

PubMed

Lin, Xiangfeng; Fang, Jian; Chen, Menglin; Huang, Zhi; Su, Chengyuan

2016-08-01

An efficient adsorbent/catalyst Co and Fe-catalysts loaded on sepiolite (Co-Fe/sepiolite) was successfully prepared for high temperature gas flow catalytic reaction by a simple impregnation method. The impact of preparation conditions (such as pH value of impregnation solution, impregnation time, calcination temperature, and time) on catalytic activity was studied. We found that the catalytic activity of Co-Fe/sepiolite was strongly influenced by all the investigated parameters. The regeneration efficiency (RE) was used to evaluate the catalytic activity. The RE is more noticeable at pH 5.0 of impregnation solution, impregnation time 18 h, calcination temperature 650 °C, and calcination time 3 h. This Co-Fe/sepiolite has great adsorption capacity in absorbing dye. It is used for an adsorbent to adsorb dye from wastewater solution under dynamic adsorption and saturated with dye, then regenerated with high temperature gas flow for adsorption/oxidation cycles. The Co-Fe/sepiolite acts as a catalyst to degrade the dye during regeneration under high temperature gas flow. Hence, the Co-Fe/sepiolite is not only an adsorbent but also a catalyst. The Co-Fe/sepiolite is more stable than sepiolite when applied in the treatment of plant's wastewater. The Co-Fe/sepiolite can be reused in adsorption-regeneration cycle. The results indicate the usability of the proposed combined process, dye adsorption on Co-Fe/sepiolite followed by the catalytic oxidation in high temperature gas flow.

Two-phase damping and interface surface area in tubes with vertical internal flow

NASA Astrophysics Data System (ADS)

Béguin, C.; Anscutter, F.; Ross, A.; Pettigrew, M. J.; Mureithi, N. W.

2009-01-01

Two-phase flow is common in the nuclear industry. It is a potential source of vibration in piping systems. In this paper, two-phase damping in the bubbly flow regime is related to the interface surface area and, therefore, to flow configuration. Experiments were performed with a vertical tube clamped at both ends. First, gas bubbles of controlled geometry were simulated with glass spheres let to settle in stagnant water. Second, air was injected in stagnant alcohol to generate a uniform and measurable bubble flow. In both cases, the two-phase damping ratio is correlated to the number of bubbles (or spheres). Two-phase damping is directly related to the interface surface area, based on a spherical bubble model. Further experiments were carried out on tubes with internal two-phase air-water flows. A strong dependence of two-phase damping on flow parameters in the bubbly flow regime is observed. A series of photographs attests to the fact that two-phase damping in bubbly flow increases for a larger number of bubbles, and for smaller bubbles. It is highest immediately prior to the transition from bubbly flow to slug or churn flow regimes. Beyond the transition, damping decreases. It is also shown that two-phase damping increases with the tube diameter.

Catalytic converter with fluid injector for catalyst-free enclosure of catalyst bed

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

Andrew, S.P.S.

1984-09-25

A fluid injection lozenge comprises two tubes supporting a perforate member forming a cage enclosing the space between the tubes. Each tube has a series of perforations along its length so that a fluid can be injected, through the tube, into the enclosed space. The lozenges are of use in catalytic converters of either the axial or radial flow design. In the case of a radial flow converter, a plurality of tubes are provided, preferably connected in pairs by the perforate members, to form a squirrel cage structure, disposed in the catalyst bed.

The Traffic Management Advisor

NASA Technical Reports Server (NTRS)

Nedell, William; Erzberger, Heinz; Neuman, Frank

1990-01-01

The traffic management advisor (TMA) is comprised of algorithms, a graphical interface, and interactive tools for controlling the flow of air traffic into the terminal area. The primary algorithm incorporated in it is a real-time scheduler which generates efficient landing sequences and landing times for arrivals within about 200 n.m. from touchdown. A unique feature of the TMA is its graphical interface that allows the traffic manager to modify the computer-generated schedules for specific aircraft while allowing the automatic scheduler to continue generating schedules for all other aircraft. The graphical interface also provides convenient methods for monitoring the traffic flow and changing scheduling parameters during real-time operation.

Graphical User Interface Development and Design to Support Airport Runway Configuration Management

NASA Technical Reports Server (NTRS)

Jones, Debra G.; Lenox, Michelle; Onal, Emrah; Latorella, Kara A.; Lohr, Gary W.; Le Vie, Lisa

2015-01-01

The objective of this effort was to develop a graphical user interface (GUI) for the National Aeronautics and Space Administration's (NASA) System Oriented Runway Management (SORM) decision support tool to support runway management. This tool is expected to be used by traffic flow managers and supervisors in the Airport Traffic Control Tower (ATCT) and Terminal Radar Approach Control (TRACON) facilities.

Development of GREET Catalyst Module

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

Wang, Zhichao; Benavides, Pahola T.; Dunn, Jennifer B.

2015-09-01

In this report, we develop energy and material flows for the production of five different catalysts (tar reforming, alcohol synthesis, Zeolite Socony Mobil-5 [ZSM-5], Mo/Co/ γ-Al 2O3, and Pt/ γ-Al 2O 3) and two chemicals (olivine, dimethyl ether of polyethylene glycol [DEPG]). These compounds and catalysts are now included in the Greenhouse Gases, Regulated Emissions and Energy Use in Transportation (GREET™) catalyst module.

Interface Control Specification

DOT National Transportation Integrated Search

1996-06-12

The Requirements Specification Document (#9933.04) identifies the overall system level requirements of the Gary-Chicago-Milwaukee (GCM) Corridor Transportation Information Center (C-TIC). This document provides details about the data and control flow...

Experimentally Testing Hydrothermal Vent Origin of Life on Enceladus and Other Icy/Ocean Worlds.

PubMed

Barge, Laura M; White, Lauren M

2017-09-01

We review various laboratory strategies and methods that can be utilized to simulate prebiotic processes and origin of life in hydrothermal vent systems on icy/ocean worlds. Crucial steps that could be simulated in the laboratory include simulations of water-rock chemistry (e.g., serpentinization) to produce hydrothermal fluids, the types of mineral catalysts and energy gradients produced in vent interfaces where hydrothermal fluids interface with the surrounding seawater, and simulations of biologically relevant chemistry in flow-through gradient systems (i.e., far-from-equilibrium experiments). We describe some examples of experimental designs in detail, which are adaptable and could be used to test particular hypotheses about ocean world energetics or mineral/organic chemistry. Enceladus among the ocean worlds provides an ideal test case, since the pressure at the ocean floor is more easily simulated in the lab. Results for Enceladus could be extrapolated with further experiments and modeling to understand other ocean worlds. Key Words: Enceladus-Ocean worlds-Icy worlds-Hydrothermal vent-Iron sulfide-Gradient. Astrobiology 17, 820-833.

Locus-specific microemulsion catalysts for sulfur mustard (HD) chemical warfare agent decontamination.

PubMed

Fallis, Ian A; Griffiths, Peter C; Cosgrove, Terence; Dreiss, Cecile A; Govan, Norman; Heenan, Richard K; Holden, Ian; Jenkins, Robert L; Mitchell, Stephen J; Notman, Stuart; Platts, Jamie A; Riches, James; Tatchell, Thomas

2009-07-22

The rates of catalytic oxidative decontamination of the chemical warfare agent (CWA) sulfur mustard (HD, bis(2-chlororethyl) sulfide) and a range (chloroethyl) sulfide simulants of variable lipophilicity have been examined using a hydrogen peroxide-based microemulsion system. SANS (small-angle neutron scattering), SAXS (small-angle X-ray scattering), PGSE-NMR (pulsed-gradient spin-echo NMR), fluorescence quenching, and electrospray mass spectroscopy (ESI-MS) were implemented to examine the distribution of HD, its simulants, and their oxidation/hydrolysis products in a model oil-in-water microemulsion. These measurements not only present a means of interpreting decontamination rates but also a rationale for the design of oxidation catalysts for these toxic materials. Here we show that by localizing manganese-Schiff base catalysts at the oil droplet-water interface or within the droplet core, a range of (chloroethyl) sulfides, including HD, spanning some 7 orders of octanol-water partition coefficient (K(ow)), may be oxidized with equal efficacy using dilute (5 wt. % of aqueous phase) hydrogen peroxide as a noncorrosive, environmentally benign oxidant (e.g., t(1/2) (HD) approximately 18 s, (2-chloroethyl phenyl sulfide, C(6)H(5)SCH(2)CH(2)Cl) approximately 15 s, (thiodiglycol, S(CH(2)CH(2)OH)(2)) approximately 19 s {20 degrees C}). Our observations demonstrate that by programming catalyst lipophilicity to colocalize catalyst and substrate, the inherent compartmentalization of the microemulsion can be exploited to achieve enhanced rates of reaction or to exert control over product selectivity. A combination of SANS, ESI-MS and fluorescence quenching measurements indicate that the enhanced catalytic activity is due to the locus of the catalyst and not a result of partial hydrolysis of the substrate.

Development of an advanced Sabatier CO2 reduction subsystem

NASA Technical Reports Server (NTRS)

Kleiner, G. N.; Cusick, R. J.

1981-01-01

A preprototype Sabatier CO2 reduction subsystem was successfully designed, fabricated and tested. The lightweight, quick starting (less than 5 minutes) reactor utlizes a highly active and physically durable methanation catalyst composed of ruthenium on alumina. The use of this improved catalyst permits a simple, passively controlled reactor design with an average lean component H2/CO2 conversion efficiency of over 99% over a range of H2/CO2 molar ratios of 1.8 to 5 while operating with process flows equivalent to a crew size of up to five persons. The subsystem requires no heater operation after start-up even during simulated 55 minute lightside/39 minute darkside orbital operation.

Submergible torch for treating waste solutions and method thereof

DOEpatents

Mattus, A.J.

1994-12-06

A submergible torch is described for removing nitrate and/or nitrite ions from a waste solution containing nitrate and/or nitrite ions comprises: a torch tip, a fuel delivery mechanism, a fuel flow control mechanism, a catalyst, and a combustion chamber. The submergible torch is ignited to form a flame within the combustion chamber of the submergible torch. The torch is submerged in a waste solution containing nitrate and/or nitrite ions in such a manner that the flame is in contact with the waste solution and the catalyst and is maintained submerged for a period of time sufficient to decompose the nitrate and/or nitrite ions present in the waste solution. 2 figures.

Growth of graphene films from non-gaseous carbon sources

DOEpatents

Tour, James; Sun, Zhengzong; Yan, Zheng; Ruan, Gedeng; Peng, Zhiwei

2015-08-04

In various embodiments, the present disclosure provides methods of forming graphene films by: (1) depositing a non-gaseous carbon source onto a catalyst surface; (2) exposing the non-gaseous carbon source to at least one gas with a flow rate; and (3) initiating the conversion of the non-gaseous carbon source to the graphene film, where the thickness of the graphene film is controllable by the gas flow rate. Additional embodiments of the present disclosure pertain to graphene films made in accordance with the methods of the present disclosure.

Hydrogen Doping into MoO3 Supports toward Modulated Metal-Support Interactions and Efficient Furfural Hydrogenation on Iridium Nanocatalysts.

PubMed

Xie, Lifang; Chen, Ting; Chan, Hang Cheong; Shu, Yijin; Gao, Qingsheng

2018-03-16

As promising supports, reducible metal oxides afford strong metal-support interactions to achieve efficient catalysis, which relies on their band states and surface stoichiometry. In this study, in situ and controlled hydrogen doping (H doping) by means of H 2 spillover was employed to engineer the metal-support interactions in hydrogenated MoO x -supported Ir (Ir/H-MoO x ) catalysts and thus promote furfural hydrogenation to furfuryl alcohol. By easily varying the reduction temperature, the resulting H doping in a controlled manner tailors low-valence Mo species (Mo 5+ and Mo 4+ ) on H-MoO x supports, thereby promoting charge redistribution on Ir and H-MoO x interfaces. This further leads to clear differences in H 2 chemisorption on Ir, which illustrates its potential for catalytic hydrogenation. As expected, the optimal Ir/H-MoO x with controlled H doping afforded high activity (turnover frequency: 4.62 min -1 ) and selectivity (>99 %) in furfural hydrogenation under mild conditions (T=30 °C, PH2 =2 MPa), which means it performs among the best of current catalysts. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Experimental and modeling study of high performance direct carbon solid oxide fuel cell with in situ catalytic steam-carbon gasification reaction

NASA Astrophysics Data System (ADS)

Xu, Haoran; Chen, Bin; Zhang, Houcheng; Tan, Peng; Yang, Guangming; Irvine, John T. S.; Ni, Meng

2018-04-01

In this paper, 2D models for direct carbon solid oxide fuel cells (DC-SOFCs) with in situ catalytic steam-carbon gasification reaction are developed. The simulation results are found to be in good agreement with experimental data. The performance of DC-SOFCs with and without catalyst are compared at different operating potential, anode inlet gas flow rate and operating temperature. It is found that adding suitable catalyst can significantly speed up the in situ steam-carbon gasification reaction and improve the performance of DC-SOFC with H2O as gasification agent. The potential of syngas and electricity co-generation from the fuel cell is also evaluated, where the composition of H2 and CO in syngas can be adjusted by controlling the anode inlet gas flow rate. In addition, the performance DC-SOFCs and the percentage of fuel in the outlet gas are both increased with increasing operating temperature. At a reduced temperature (below 800 °C), good performance of DC-SOFC can still be obtained with in-situ catalytic carbon gasification by steam. The results of this study form a solid foundation to understand the important effect of catalyst and related operating conditions on H2O-assisted DC-SOFCs.

Optimization of Synthesis Conditions of Carbon Nanotubes via Ultrasonic-Assisted Floating Catalyst Deposition Using Response Surface Methodology

PubMed Central

Mohammadian, Narges; Ghoreishi, Seyyed M.; Hafeziyeh, Samira; Saeidi, Samrand; Dionysiou, Dionysios D.

2018-01-01

The growing use of carbon nanotubes (CNTs) in a plethora of applications has provided to us a motivation to investigate CNT synthesis by new methods. In this study, ultrasonic-assisted chemical vapor deposition (CVD) method was employed to synthesize CNTs. The difficulty of controlling the size of clusters and achieving uniform distribution—the major problem in previous methods—was solved by using ultrasonic bath and dissolving ferrocene in xylene outside the reactor. The operating conditions were optimized using a rotatable central composite design (CCD), which helped optimize the operating conditions of the method. Response surface methodology (RSM) was used to analyze these experiments. Using statistical software was very effective, considering that it decreased the number of experiments needed to achieve the optimum conditions. Synthesis of CNTs was studied as a function of three independent parameters viz. hydrogen flow rate (120–280 cm3/min), catalyst concentration (2–6 wt %), and synthesis temperature (800–1200 °C). Optimum conditions for the synthesis of CNTs were found to be 3.78 wt %, 184 cm3/min, and 976 °C for catalyst concentration, hydrogen flow rate, and synthesis temperature, respectively. Under these conditions, Raman spectrum indicates high values of (IG/ID), which means high-quality CNTs. PMID:29747451

Recent Developments of Electrochemical Promotion of Catalysis in the Techniques of DeNOx

PubMed Central

Tang, Xiaolong; Yi, Honghong; Chen, Chen; Wang, Chuan

2013-01-01

Electrochemical promotion of catalysis reactions (EPOC) is one of the most significant discoveries in the field of catalytic and environmental protection. The work presented in this paper focuses on the aspects of reaction mechanism, influencing factors, and recent positive results. It has been shown with more than 80 different catalytic systems that the catalytic activity and selectivity of conductive catalysts deposited on solid electrolytes can be altered in the last 30 years. The active ingredient of catalyst can be activated by applying constant voltage or constant current to the catalysts/electrolyte interface. The effect of EPOC can improve greatly the conversion rate of NOx. And it can also improve the lifetime of catalyst by inhibiting its poisoning. PMID:23970835

Synthesis of Biodiesel in Batch and Packed-Bed Reactors Using Powdered and Granular Sugar Catalyst

NASA Astrophysics Data System (ADS)

Janaun, J.; Lim, P. M.; Balan, W. S.; Yaser, A. Z.; Chong, K. P.

2017-06-01

Increasing world production of palm oil warrants effective utilization of its waste. In particular, conversion of waste cooking oil into biodiesel has obtained global interest because of renewable energy need and reduction of CO2 emission. In this study, oleic acid used as a model compound for waste cooking oil conversion using esterification reaction catalysed by sugar catalyst (SC) in powdered (P-SC) and granular (G-SC) forms. The catalysts were synthesized via incomplete carbonization of D-glucose followed by functionalization with concentrated sulphuric acid. Catalysts characterizations were done for their physical and chemical properties using modern tools. Batch and packed-bed reactor systems were used to evaluate the reactivity of the catalysts. The results showed that G-SC had slightly higher total acidity and more porous than P-SC. The experimental conditions for batch reaction were temperature of 60°C, molar ratio of 1:20 (Oleic Acid:Methanol) and 2 wt. catalyst with respect to oleic acid. The results showed the maximum oleic acid conversion using G-SC and P-SC were 52 and 48, respectively. Whereas, the continuous reaction with varying feed flow rate as a function of retention time was studied by using 3 g of P-SC in 60 °C and 1:20 molar ratio in a packed-bed reactor. The results showed that a longer retention time which was 6.48 min and feed flow rate 1.38 ml/min, achieved higher average conversion of 9.9 and decreased with further increasing flow rate. G-SC showed a better average conversion of 10.8 at lowest feed flow rate of 1.38 ml/min in continuous reaction experiments. In a broader perspective, large scale continuous biodiesel production is feasible using granular over powdered catalyst mainly due to it lower pressure drop.

Use of X-ray absorption near edge structure (XANES) to identify physisorption and chemisorption of phosphate onto ferrihydrite-modified diatomite.

PubMed

Xiong, Wenhui; Peng, Jian; Hu, Yongfeng

2012-02-15

This paper presents a novel technique integrating bulk-sensitive and surface-sensitive XANES methods to distinguish between physisorption and chemisorption for phosphate adsorption onto ferrihydrite-modified diatomite (FHMD). XANES P K-edge, L-edge, and Fe M-edge spectra were obtained for reference samples (K(2)HPO(4) and FePO(4)·2H(2)O) and test samples (phosphate adsorbed onto FHMD (FHMD-Ps) and Si-containing ferrihydrite (FHYD-Ps)). A resolvable pre-edge peak in the P K-edge spectra of FHMD-Ps and FHYD-Ps provided direct evidence for the formation of P-O-Fe(III) coordination and the occurrence of chemisorption. The resemblance between the P L-edge spectra of K(2)HPO(4) and FHMD-Ps and the marked difference between the spectra of FHMD-Ps and FePO(4)·2H(2)O indicated the intact existence of the adsorbate and the adsorbent. The similarity between Fe M-edge spectra of FHMD and FHMD-Ps and the difference between the spectra of FHMD-Ps and FePO(4)·2H(2)O confirmed the findings from P L-edge analyses. Therefore, chemisorption and physisorption coexisted during phosphate adsorption onto FHMD. Phosphate chemisorption occurred in the deeper zone of FHMD (from 50 nm to 5 μm); whereas physisorption occurred in the zone of FHMD shallower than 50 nm since the probing depth of XANES P K-edge method is 5 μm and that of P L-edge and Fe M-edge methods is 50 nm. Copyright © 2011 Elsevier Inc. All rights reserved.

Perch use by laying hens in a commercial aviary1

PubMed Central

Campbell, D. L. M.; Makagon, M. M.; Swanson, J. C.; Siegford, J. M.

2016-01-01

Non-cage housing systems, such as the aviary, are being implemented by the laying hen industry, including in North America, in an attempt to improve the welfare of hens. Perches are a resource that is consistently included in aviaries. Hens are strongly motivated to perch, and perching can improve leg bone strength. However, hens may prefer elevated perches, particularly at night, and thus simply providing perches is not enough to improve welfare; they must be provided in a way that allows all hens to access them. Observations of laying hens using perches and ledges (flat, solid metal shelves to assist hens’ movement between tiers) in a commercial aviary revealed variation in where hens roosted within the tiered aviary enclosure across the flock cycle (peak, mid and end of lay; P < 0.001 for all age points). Hens most often preferred roosting in the highest enclosure levels, leading to crowding on upper perches and ledges while perch space remained available on lower levels. Restricted access to preferable perches may cause frustration in hens, leading to welfare issues. Hens roosted more on perches at peak lay than mid and end lay (P < 0.001) but roosted less on ledges at peak lay than mid and end lay (P < 0.001). Additionally, more hens roosted on both perches and ledges in the ‘dark’ observation period compared with the number of hens roosting during the ‘light’ observation period (P < 0.001). Further research should look at all structural elements within the system that are used by hens for roosting, such as edges of tiers and upper wire floors, to evaluate how changes in perching preferences across the lay cycle may correlate with system design and bird-based parameters. PMID:26994206

Scale-dependent effects of habitat on movements and path structure of reef sharks at a predator-dominated atoll.

PubMed

Papastamatiou, Yannis P; Lowe, Christopher G; Caselle, Jennifer E; Friedlander, Alan M

2009-04-01

The effects of habitat on the ecology, movements, and foraging strategies of marine apex predators are largely unknown. We used acoustic telemetry to quantify the movement patterns of blacktip reef sharks (Carcharhinus melanopterus) at Palmyra Atoll National Wildlife Refuge, in the Pacific Ocean. Sharks had relatively small home ranges over a timescale of days to weeks (0.55 +/- 0.24 km2) and showed strong site fidelity to sand-flat ledges within the west lagoon over a three-year period. Sharks showed evidence of diel and tidal movements, and they utilized certain regions of the west lagoon disproportionately. There were ontogenetic shifts in habitat selection, with smaller sharks showing greater selection for sand-flat habitats, and pups (total length 35-61 cm) utilizing very shallow waters on sand-flats, potentially as nursery areas. Adult sharks selected ledge habitats and had lower rates of movement when over sand-flats and ledges than they did over lagoon waters. Fractal analysis of movements showed that over periods of days, sharks used patches that were 3-17% of the scale of their home range. Repeat horizontal movements along ledge habitats consisted of relatively straight movements, which theoretical models consider the most efficient search strategy when forage patches may be spatially and temporally unpredictable. Although sharks moved using a direct walk while in patches, they appeared to move randomly between patches. Microhabitat quantity and quality had large effects on blacktip reef shark movements, which have consequences for the life-history characteristics of the species and potentially the spatial distribution of behaviorally mediated effects on lower trophic levels throughout the Palmyra ecosystem.

Polymer membrane based electrolytic cell and process for the direct generation of hydrogen peroxide in liquid streams

NASA Technical Reports Server (NTRS)

White, James H. (Inventor); Schwartz, Michael (Inventor); Sammells, Anthony F. (Inventor)

1997-01-01

An electrolytic cell for generating hydrogen peroxide is provided including a cathode containing a catalyst for the reduction of oxygen, and an anode containing a catalyst for the oxidation of water. A polymer membrane, semipermeable to either protons or hydroxide ions is also included and has a first face interfacing to the cathode and a second face interfacing to the anode so that when a stream of water containing dissolved oxygen or oxygen bubbles is passed over the cathode and a stream of water is passed over the anode, and an electric current is passed between the anode and the cathode, hydrogen peroxide is generated at the cathode and oxygen is generated at the anode.

Heterogeneous Pd catalysts as emulsifiers in Pickering emulsions for integrated multistep synthesis in flow chemistry

PubMed Central

Hiebler, Katharina; Lichtenegger, Georg J; Maier, Manuel C; Park, Eun Sung; Gonzales-Groom, Renie

2018-01-01

Within the “compartmentalised smart factory” approach of the ONE-FLOW project the implementation of different catalysts in “compartments” provided by Pickering emulsions and their application in continuous flow is targeted. We present here the development of heterogeneous Pd catalysts that are ready to be used in combination with biocatalysts for catalytic cascade synthesis of active pharmaceutical ingredients (APIs). In particular, we focus on the application of the catalytic systems for Suzuki–Miyaura cross-coupling reactions, which is the key step in the synthesis of the targeted APIs valsartan and sacubitril. An immobilised enzyme will accomplish the final product formation via hydrolysis. In order to create a large interfacial area for the catalytic reactions and to keep the reagents separated until required, the catalyst particles are used to stabilise Pickering emulsions of oil and water. A set of Ce–Sn–Pd oxides with the molecular formula Ce0.99− xSnxPd0.01O2−δ (x = 0–0.99) has been prepared utilising a simple single-step solution combustion method. The high applicability of the catalysts for different functional groups and their minimal leaching behaviour is demonstrated with various Suzuki–Miyaura cross-coupling reactions in batch as well as in continuous flow employing the so-called “plug & play reactor”. Finally, we demonstrate the use of these particles as the sole emulsifier of oil–water emulsions for a range of oils. PMID:29623127

Electrohydrodynamic controlled assembly and fracturing of thin colloidal particle films confined at drop interfaces

NASA Astrophysics Data System (ADS)

Rozynek, Z.; Dommersnes, P.; Mikkelsen, A.; Michels, L.; Fossum, J. O.

2014-09-01

Particles can adsorb strongly at liquid interfaces due to capillary forces, which in practice can confine the particles to the interface. Here we investigate the electrohydrodynamic flow driven packing and deformation of colloidal particle layers confined at the surface of liquid drops. The electrohydrodynamic flow has a stagnation point at the drop equator, leading to assembly of particles in a ribbon shaped film. The flow is entirely controlled by the electric field, and we demonstrate that AC fields can be used to induce hydrodynamic "shaking" of the colloidal particle film. We find that the mechanical properties of the film is highly dependent on the particles: monodisperse polystyrene beads form packed granular monolayers which "liquefies" upon shaking, whereas clay mineral particles form cohesive films that fracture upon shaking. The results are expected to be relevant for understanding the mechanics and rheology of particle stabilized emulsions. Supplementary material in the form of a pdf file available from the Journal web page at http://dx.doi.org/10.1140/epjst/e2014-02231-x

Direct numerical simulations of agglomeration of circular colloidal particles in two-dimensional shear flow

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

Choi, Young Joon, E-mail: yjchoi@uvic.ca; Djilali, Ned, E-mail: ndjilali@uvic.ca

2016-01-15

Colloidal agglomeration of nanoparticles in shear flow is investigated by solving the fluid-particle and particle-particle interactions in a 2D system. We use an extended finite element method in which the dynamics of the particles is solved in a fully coupled manner with the flow, allowing an accurate description of the fluid-particle interfaces without the need of boundary-fitted meshes or of empirical correlations to account for the hydrodynamic interactions between the particles. Adaptive local mesh refinement using a grid deformation method is incorporated with the fluid-structure interaction algorithm, and the particle-particle interaction at the microscopic level is modeled using the Lennard-Jonesmore » potential. Motivated by the process used in fabricating fuel cell catalysts from a colloidal ink, the model is applied to investigate agglomeration of colloidal particles under external shear flow in a sliding bi-periodic Lees-Edwards frame with varying shear rates and particle fraction ratios. Both external shear and particle fraction are found to have a crucial impact on the structure formation of colloidal particles in a suspension. Segregation intensity and graph theory are used to analyze the underlying agglomeration patterns and structures, and three agglomeration regimes are identified.« less

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

PubMed

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

2017-12-24

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

Impact of Silicon Nanocrystal Oxidation on the Nonmetallic Growth of Carbon Nanotubes.

PubMed

Rocks, Conor; Mitra, Somak; Macias-Montero, Manuel; Maguire, Paul; Svrcek, Vladimir; Levchenko, Igor; Ostrikov, Kostya; Mariotti, Davide

2016-07-27

Carbon nanotube (CNT) growth has been demonstrated recently using a number of nonmetallic semiconducting and metal oxide nanoparticles, opening up pathways for direct CNT synthesis from a number of more desirable templates without the need for metallic catalysts. However, CNT growth mechanisms using these nonconventional catalysts has been shown to largely differ and reamins a challenging synthesis route. In this contribution we show CNT growth from partially oxidized silicon nanocrystals (Si NCs) that exhibit quantum confinement effects using a microwave plasma enhanced chemical vapor deposition (PECVD) method. On the basis of solvent and a postsynthesis frgamentation process, we show that oxidation of our Si NCs can be easily controlled. We determine experimentally and explain with theoretical simulations that the Si NCs morphology together with a necessary shell oxide of ∼1 nm is vital to allow for the nonmetallic growth of CNTs. On the basis of chemical analysis post-CNT-growth, we give insight into possible mechanisms for CNT nucleation and growth from our partially oxidized Si NCs. This contribution is of significant importance to the improvement of nonmetallic catalysts for CNT growth and the development of Si NC/CNT interfaces.

Synergistically Enhanced Electrochemical Performance of Ni3S4-PtX (X = Fe, Ni) Heteronanorods as Heterogeneous Catalysts in Dye-Sensitized Solar Cells.

PubMed

Huang, Shoushuang; Ma, Dui; Hu, ZhangJun; He, Qingquan; Zai, Jiantao; Chen, Dayong; Sun, Huai; Chen, Zhiwen; Qiao, Qiquan; Wu, Minghong; Qian, Xuefeng

2017-08-23

Platinum (Pt)-based alloys are considerably promising electrocatalysts for the reduction of I - /I 3 - and Co 2+ /Co 3+ redox couples in dye-sensitized solar cells (DSSCs). However, it is still challenging to minimize the dosage of Pt to achieve comparable or even higher catalytic efficiency. Here, by taking full advantages of the Mott-Schottky (M-S) effect at the metal-semiconductor interface, we successfully strategize a low-Pt-based M-S catalyst with enhanced electrocatalytic performance and stability for the large-scale application of DSSCs. The optimized M-S electrocatalyst of Ni 3 S 4 -Pt 2 X 1 (X = Fe, Ni) heteronanorods is constructed by rationally controlling the ratio of Pt to transition metal in the hybrids. It was found that the electrons transferred from Ni 3 S 4 to Pt 2 X 1 at their interface under the Mott-Schottky effect result in the concentration of electrons onto Pt 2 X 1 domains, which subsequently accelerates the regeneration of both I - /I 3 - and Co 2+ /Co 3+ redox shuttles in DSSCs. As a result, the DSSC with Ni 3 S 4 -Pt 2 Fe 1 manifests an impressive power conversion efficiency (PCE) of 8.79% and 5.56% for iodine and cobalt-based electrolyte under AM1.5G illumination, respectively. These PCEs are obviously superior over those with Ni 3 S 4 -Pt, PtFe, Ni 3 S 4 , and pristine Pt electrodes. The strategy reported here is able to be further expanded to fabricate other low-Pt-alloyed M-S catalysts for wider applications in the fields of photocatalysis, water splitting, and heterojunction solar cells.

Revealing the Dynamics of Platinum Nanoparticle Catalysts on Carbon in Oxygen and Water Using Environmental TEM

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

Luo, Langli; Engelhard, Mark H.; Shao, Yuyan

Deactivation of supported metal nanoparticle catalysts, especially in relevant gas condition, is a critical challenge for many technological applications, including heterogeneous catalysis, electrocatalysis, fuel cells, biomedical imaging and drug delivery. It has been far more commonly realized that deactivation of catalysts stems from surface area loss due to particle coarsening, however, for which the mechanism remains largely unclear. Herein, we use aberration corrected environmental transmission electron microscopy, at atomic level, to in-situ observe the dynamics of Pt catalyst in fuel cell relevant gas conditions. Particles migration and coalescence is observed to be the dominant coarsening process. As compared with themore » case of H2O, O2 promotes Pt nanoparticle migration on carbon surface. Surprisingly, coating Pt/carbon with a nanofilm of electrolyte (Nafion ionomer) leads to a faster migration of Pt in H2O than in O2, a consequence of Nafion-carbon interface water “lubrication” effect. Atomically, the particles coalescence is featured by re-orientation of particles towards lattice matching, a process driven by orientation dependent van der Waals force. These results provide direct observations of dynamics of metal nanoparticles at critical surface/interface under relevant conditions and yield significant insights into the multi-phase interaction in related technological processes.« less

Highly porous non-precious bimetallic electrocatalysts for efficient hydrogen evolution

DOE PAGES

Lu, Qi; Hutchings, Gregory S.; Yu, Weiting; ...

2015-03-16

One of the key components of carbon dioxide-free hydrogen production is a robust and efficient non-precious metal catalyst for the hydrogen evolution reaction. We report that a hierarchical nanoporous copper-titanium bimetallic electrocatalyst is able to produce hydrogen from water under a mild overpotential at more than twice the rate of state-of-the- art carbon-supported platinum catalyst. Although both copper and titanium are known to be poor hydrogen evolution catalysts, the combination of these two elements creates unique copper-copper-titanium hollow sites, which have a hydrogen-binding energy very similar to that of platinum, resulting in an exceptional hydrogen evolution activity. Moreover, the hierarchicalmore » porosity of the nanoporous-copper titanium catalyst also contributes to its high hydrogen evolution activity, because it provides a large-surface area for electrocatalytic hydrogen evolution, and improves the mass transport properties. Moreover, the catalyst is self-supported, eliminating the overpotential associated with the catalyst/support interface.« less

Geometric flow control of shear bands by suppression of viscous sliding

NASA Astrophysics Data System (ADS)

Sagapuram, Dinakar; Viswanathan, Koushik; Mahato, Anirban; Sundaram, Narayan K.; M'Saoubi, Rachid; Trumble, Kevin P.; Chandrasekar, Srinivasan

2016-08-01

Shear banding is a plastic flow instability with highly undesirable consequences for metals processing. While band characteristics have been well studied, general methods to control shear bands are presently lacking. Here, we use high-speed imaging and micro-marker analysis of flow in cutting to reveal the common fundamental mechanism underlying shear banding in metals. The flow unfolds in two distinct phases: an initiation phase followed by a viscous sliding phase in which most of the straining occurs. We show that the second sliding phase is well described by a simple model of two identical fluids being sheared across their interface. The equivalent shear band viscosity computed by fitting the model to experimental displacement profiles is very close in value to typical liquid metal viscosities. The observation of similar displacement profiles across different metals shows that specific microstructure details do not affect the second phase. This also suggests that the principal role of the initiation phase is to generate a weak interface that is susceptible to localized deformation. Importantly, by constraining the sliding phase, we demonstrate a material-agnostic method-passive geometric flow control-that effects complete band suppression in systems which otherwise fail via shear banding.

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

PubMed

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

2011-07-01

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

Final Environmental Impact Statement (As Amended 18 January 1972) Minnesota River, Minnesota, Mankato-North Mankato-Le Hillier. Flood Control. Phase I. Final Supplement II-A.

DTIC Science & Technology

1982-10-01

infeasibility of raising the down- stream rigid, multi-span, reinforced concrete arch bridge (4952) was acknow- ledged early, and study centered on the...Alternatives lB and IC center on the following issues and concerns: project costs, neighborhoods, property acquisitions and displacements, historic...and out of feeding, spawning, breeding. and nursery areas - Habitat in the fill area is not conducive for such acti- vities. Fill activities are not

Droplet Deformation in an Extensional Flow: The Role of Surfactant Physical Chemistry

NASA Technical Reports Server (NTRS)

Stebe, Kathleen J.

1996-01-01

Surfactant-induced Marangoni effects strongly alter the stresses exerted along fluid particle interfaces. In low gravity processes, these stresses can dictate the system behavior. The dependence of Marangoni effects on surfactant physical chemistry is not understood, severely impacting our ability to predict and control fluid particle flows. A droplet in an extensional flow allows the controlled study of stretching and deforming interfaces. The deformations of the drop allow both Marangoni stresses, which resist tangential shear, and Marangoni elasticities, which resist surface dilatation, to develop. This flow presents an ideal model system for studying these effects. Prior surfactant-related work in this flow considered a linear dependence of the surface tension on the surface concentration, valid only at dilute surface concentrations, or a non-linear framework at concentrations sufficiently dilute that the linear approximation was valid. The linear framework becomes inadequate for several reasons. The finite dimensions of surfactant molecules must be taken into account with a model that includes surfaces saturation. Nonideal interactions between adsorbed surfactant molecules alter the partitioning of surfactant between the bulk and the interface, the dynamics of surfactant adsorptive/desorptive exchange, and the sensitivity of the surface tension to adsorbed surfactant. For example, cohesion between hydrocarbon chains favors strong adsorption. Cohesion also slows the rate of desorption from interfaces, and decreases the sensitivity of the surface tension to adsorbed surfactant. Strong cohesive interactions result in first order surface phase changes with a plateau in the surface tension vs surface concentration. Within this surface concentration range, the surface tension is decoupled from surface concentration gradients. We are engaged in the study of the role of surfactant physical chemistry in determining the Marangoni stresses on a drop in an extensional flow in a numerical and experimental program. Using surfactants whose dynamics and equilibrium behavior have been characterized in our laboratory, drop deformation will be studied in ground-based experiment. In an accompanying numerical study, predictive drop deformations will be determined based on the isotherm and equation of state determined in our laboratory. This work will improve our abilities to predict and control all fluid particle flows.

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.

In-Water and Neat Batch and Continuous-Flow Direct Esterification and Transesterification by a Porous Polymeric Acid Catalyst

NASA Astrophysics Data System (ADS)

Baek, Heeyoel; Minakawa, Maki; Yamada, Yoichi M. A.; Han, Jin Wook; Uozumi, Yasuhiro

2016-05-01

A porous phenolsulphonic acid—formaldehyde resin (PAFR) was developed. The heterogeneous catalyst PAFR was applied to the esterification of carboxylic acids and alcohols, affording the carboxylic acid esters in a yield of up to 95% where water was not removed from the reaction mixture. Surprisingly, the esterification in water as a solvent proceeded to afford the desired esters in high yield. PAFR provided the corresponding esters in higher yield than other homogeneous and heterogeneous catalysts. The transesterification of alcohols and esters was also investigated by using PAFR, giving the corresponding esters. PAFR was applied to the batch-wise and continuous-flow production of biodiesel fuel FAME. The PAFR-packed flow reactor that was developed for the synthesis of carboxylic acids and FAME worked for four days without loss of its catalytic activity.

Catalytic ignition of hydrogen and oxygen propellants

NASA Technical Reports Server (NTRS)

Zurawski, Robert L.; Green, James M.

1988-01-01

An experimental program was conducted to evaluate the catalytic ignition of gaseous hydrogen and oxygen propellants. Shell 405 granular catalyst and a monolithic sponge catalyst were tested. Mixture ratio, mass flow rate, propellant temperature, and back pressure were varied parametrically in testing to determine the operational limits of the catalytic igniter. The test results show that the gaseous hydrogen and oxygen propellant combination can be ignited catalytically using Shell 405 catalyst over a wide range of mixture ratios, mass flow rates, and propellant injection temperatures. These operating conditions must be optimized to ensure reliable ignition for an extended period of time. A cyclic life of nearly 2000, 2 sec pulses at nominal operating conditions was demonstrated with the catalytic igniter. The results of the experimental program and the established operational limits for a catalytic igniter using the Shell 405 catalysts are presented.

Catalytic ignition of hydrogen and oxygen propellants

NASA Technical Reports Server (NTRS)

Zurawski, Robert L.; Green, James M.

1988-01-01

An experimental program was conducted to evaluate the catalytic ignition of gaseous hydrogen and oxygen propellants. Shell 405 granular catalyst and a monolithic sponge catalyst were tested. Mixture ratio, mass flow rate, propellant temperature, and back pressure were varied parametrically in testing to determine the operational limits of the catalytic igniter. The test results show that the gaseous hydrogen and oxygen propellant combination can be ignited catalytically using Shell 405 catalyst over a wide range of mixture ratios, mass flow rates, and propellant injection temperatures. These operating conditions must be optimized to ensure reliable ignition for an extended period of time. A cyclic life of nearly 2000, 2 sec pulses at nominal operating conditions was demonstrated with the catalytic igniter. The results of the experimental program and the established operational limits for a catalytic igniter using the Shell 405 catalyst are presented.

Pump and Flow Control Subassembly of Thermal Control Subsystem for Photovoltaic Power Module

NASA Technical Reports Server (NTRS)

Motil, Brian; Santen, Mark A.

1993-01-01

The pump and flow control subassembly (PFCS) is an orbital replacement unit (ORU) on the Space Station Freedom photovoltaic power module (PVM). The PFCS pumps liquid ammonia at a constant rate of approximately 1170 kg/hr while providing temperature control by flow regulation between the radiator and the bypass loop. Also, housed within the ORU is an accumulator to compensate for fluid volumetric changes as well as the electronics and firmware for monitoring and control of the photovoltaic thermal control system (PVTCS). Major electronic functions include signal conditioning, data interfacing and motor control. This paper will provide a description of each major component within the PFCS along with performance test data. In addition, this paper will discuss the flow control algorithm and describe how the nickel hydrogen batteries and associated power electronics will be thermally controlled through regulation of coolant flow to the radiator.

In situ NAP-XPS spectroscopy during methane dry reforming on ZrO2/Pt(1 1 1) inverse model catalyst

NASA Astrophysics Data System (ADS)

Rameshan, C.; Li, H.; Anic, K.; Roiaz, M.; Pramhaas, V.; Rameshan, R.; Blume, R.; Hävecker, M.; Knudsen, J.; Knop-Gericke, A.; Rupprechter, G.

2018-07-01

Due to the need of sustainable energy sources, methane dry reforming is a useful reaction for conversion of the greenhouse gases CH4 and CO2 to synthesis gas (CO  +  H2). Syngas is the basis for a wide range of commodity chemicals and can be utilized for fuel production via Fischer–Tropsch synthesis. The current study focuses on spectroscopic investigations of the surface and reaction properties of a ZrO2/Pt inverse model catalyst, i.e. ZrO2 particles (islands) grown on a Pt(1 1 1) single crystal, with emphasis on in situ near ambient pressure x-ray photoelectron spectroscopy (NAP-XPS) during MDR reaction. In comparison to technological systems, model catalysts facilitate characterization of the surface (oxidation) state, surface adsorbates, and the role of the metal-support interface. Using XPS and infrared reflection absorption spectroscopy we demonstrated that under reducing conditions (UHV or CH4) the ZrO2 particles transformed to an ultrathin ZrO2 film that started to cover (wet) the Pt surface in an SMSI-like fashion, paralleled by a decrease in surface/interface oxygen. In contrast, (more oxidizing) dry reforming conditions with a 1:1 ratio of CH4 and CO2 were stabilizing the ZrO2 particles on the model catalyst surface (or were even reversing the strong metal support interaction (SMSI) effect), as revealed by in situ XPS. Carbon deposits resulting from CH4 dissociation were easily removed by CO2 or by switching to dry reforming conditions (673–873 K). Thus, at these temperatures the active Pt surface remained free of carbon deposits, also preserving the ZrO2/Pt interface.

A helical biosonar scanning pattern in the Chinese noctule, Nyctalus plancyi.

PubMed

Müller, Rolf; Lu, Hongwang; Zhang, Shuyi; Peremans, Herbert

2006-06-01

Directivity and sound diffraction of the pinna of the Chinese Noctule (Nyctalus plancyi) have been studied numerically. The pinna was found capable of generating a periodic helical scanning pattern over frequency, if the tragus and the thickened lower ledge of the pinna rim were in an appropriate position. During the helical scan, a directivity pattern with a strong mainlobe alternated with a pattern dominated by a conical sleeve of sidelobes. This alternation was present, even when an unfavorable arrangement of the pinna disrupted the overall helical scanning pattern. In the fully formed helical scan, the orientation of main and sidelobes for different frequencies revealed a spatial ordering which extends volume coverage. Five different pinna parts have been removed from the digital pinna-shape representations in turn to assess their influence on the directivity. Of these parts, the tragus stem and the thickened lower ledge of the pinna rim were found to have the largest overall impact. The anatomical prominence of these structures was hence in agreement with their acoustic functionality. In the near-field, tragus stem and lower ledge were seen to act primarily through large shifts in the wavefield phase in both directions.

Manganese L-edge X-ray absorption spectroscopy of manganese catalase from Lactobacillus plantarum and mixed valence manganese complexes

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

Grush, M.M.; Chen, J.; George, S.J.

1996-01-10

The first Mn L-edge absorption spectra of a Mn metalloprotein are presented in this paper. Both reduced and superoxidized Mn catalase have been examined by fluorescence-detected soft X-ray absorption spectroscopy, and their Mn L-edge spectra are dramatically different. The spectrum of reduced Mn(II)Mn(II) catalase has been interpreted by ligand field atomic multiplet calculations and by comparison to model compound spectra. The analysis finds a 10 Dq value of nearly 1.1 eV, consistent with coordination by predominately nitrogen and oxygen donor ligands. For interpretation of mixed valence Mn spectra, an empirical simulation procedure based on the addition of homovalent model compoundmore » spectra has been developed and was tested on a variety of Mn complexes and superoxidized Mn catalase. This routine was also used to determine the oxidation state composition of the Mn in [Ba{sub 8}Na{sub 2}ClMn{sub 16}(OH){sub 8}(CO{sub 3}){sub 4}L{sub 8}] .53 H{sub 2}O (L=1,3-diamino-2-hydroxypropane-N,N,N`N`-tetraacetic acid). 27 refs., 6 figs.« less

Effect of internal flow and evaporation on hydrogel assembly process at droplet interface

NASA Astrophysics Data System (ADS)

Kang, Giho; Seong, Baekhoon; Gim, Yeonghyeon; Ko, Han Seo; Byun, Doyoung

2017-11-01

Recently, controlling the behavior of nanoparticles inside liquid droplet has been widely studied. There have been many reports about the mechanism of the nanoparticles assembly and fabrication of a thin film on a substrate. However, the assembly mechanism at a liquid-air interface has not been clearly understood to form polymer chains into films. Herein, we investigated the role of internal flow on the thin film assembly process at the interface of the hydrogel droplet. The internal fluid flow during the formation of the hydrogel film was visualized systematically using micro-PIV (Particle image velocimetry) technique at various temperatures. We show that the buoyancy effect and convection flow induced by heat can affect the film morphology and its mechanical characteristics. Due to the accelerated fluid flow inside the droplet and evaporation flux, densely assembled hydrogel film was able to be formed. Film strength was increased 24% with temperature increase from 40 to 80 degrees Celsius. We expect our investigations could be applied to many applications such as self-assembly of planar structures at the interface in coating and printing process. The support from the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (NRF-2015R1A2A1A05001829) is acknowledged.

The effect of visualizing the flow of multimedia content among and inside devices.

PubMed

Lee, Dong-Seok

2009-05-01

This study introduces a user interface, referred to as the flow interface, which provides a graphical representation of the movement of content among and inside audio/video devices. The proposed interface provides a different frame of reference with content-oriented visualization of the generation, manipulation, storage, and display of content as well as input and output. The flow interface was applied to a VCR/DVD recorder combo, one of the most complicated consumer products. A between-group experiment was performed to determine whether the flow interface helps users to perform various tasks and to examine the learning effect of the flow interface, particularly in regard to hooking up and recording tasks. The results showed that participants with access to the flow interface performed better in terms of success rate and elapsed time. In addition, the participants indicated that they could easily understand the flow interface. The potential of the flow interface for application to other audio video devices, and design issues requiring further consideration, are discussed.

CATALYTIC RECOMBINER FOR A NUCLEAR REACTOR

DOEpatents

King, L.D.P.

1960-07-01

A hydrogen-oxygen recombiner is described for use with water-boiler type reactors. The catalyst used is the wellknown platinized alumina, and the novelty lies in the structural arrangement used to prevent flashback through the gas input system. The recombiner is cylindrical, the gases at the input end being deflected by a baffle plate through a first flashback shield of steel shot into an annular passage adjacent to and extending the full length of the housing. Below the baffle plate the gases flow first through an outer annular array of alumina pellets which serve as a second flashback shield, a means of distributing the flowing gases evenly and as a means of reducing radiation losses to the walls. Thereafter the gases flow inio the centrally disposed catalyst bed where recombination is effected. The steam and uncombined gases flow into a centrally disposed cylindrical passage inside the catalyst bod and thereafter out through the exit port. A high rate of recombination is effected.

Design and Control of Glycerol-tert-Butyl Alcohol Etherification Process

PubMed Central

Vlad, Elena; Bozga, Grigore

2012-01-01

Design, economics, and plantwide control of a glycerol-tert-butyl alcohol (TBA) etherification plant are presented. The reaction takes place in liquid phase, in a plug flow reactor, using Amberlyst 15 as a catalyst. The products' separation is achieved by two distillation columns where high-purity ethers are obtained and a section involving extractive distillation with 1,4-butanediol as solvent, which separates TBA from the TBA/water azeotrope. Details of design performed in AspenPlus and an economic evaluation of the process are given. Three plantwide control structures are examined using a mass balance model of the plant. The preferred control structure fixes the fresh glycerol flow rate and the ratio glycerol + monoether : TBA at reactor-inlet. The stability and robustness in the operation are checked by rigorous dynamic simulation in AspenDynamics. PMID:23365512

A graphical modeling tool for evaluating nitrogen loading to and nitrate transport in ground water in the mid-Snake region, south-central Idaho

USGS Publications Warehouse

Clark, David W.; Skinner, Kenneth D.; Pollock, David W.

2006-01-01

A flow and transport model was created with a graphical user interface to simplify the evaluation of nitrogen loading and nitrate transport in the mid-Snake region in south-central Idaho. This model and interface package, the Snake River Nitrate Scenario Simulator, uses the U.S. Geological Survey's MODFLOW 2000 and MOC3D models. The interface, which is enabled for use with geographic information systems (GIS), was created using ESRI's royalty-free MapObjects LT software. The interface lets users view initial nitrogen-loading conditions (representing conditions as of 1998), alter the nitrogen loading within selected zones by specifying a multiplication factor and applying it to the initial condition, run the flow and transport model, and view a graphical representation of the modeling results. The flow and transport model of the Snake River Nitrate Scenario Simulator was created by rediscretizing and recalibrating a clipped portion of an existing regional flow model. The new subregional model was recalibrated with newly available water-level data and spring and ground-water nitrate concentration data for the study area. An updated nitrogen input GIS layer controls the application of nitrogen to the flow and transport model. Users can alter the nitrogen application to the flow and transport model by altering the nitrogen load in predefined spatial zones contained within similar political, hydrologic, and size-constrained boundaries.

Isotope exchange in oxide-containing catalyst

NASA Technical Reports Server (NTRS)

Brown, Kenneth G. (Inventor); Upchurch, Billy T. (Inventor); Hess, Robert V. (Inventor); Miller, Irvin M. (Inventor); Schryer, David R. (Inventor); Sidney, Barry D. (Inventor); Wood, George M. (Inventor); Hoyt, Ronald F. (Inventor)

1989-01-01

A method of exchanging rare-isotope oxygen for common-isotope oxygen in the top several layers of an oxide-containing catalyst is disclosed. A sample of an oxide-containing catalyst is exposed to a flowing stream of reducing gas in an inert carrier gas at a temperature suitable for the removal of the reactive common-isotope oxygen atoms from the surface layer or layers of the catalyst without damaging the catalyst structure. The reduction temperature must be higher than any at which the catalyst will subsequently operate. Sufficient reducing gas is used to allow removal of all the reactive common-isotope oxygen atoms in the top several layers of the catalyst. The catalyst is then reoxidized with the desired rare-isotope oxygen in sufficient quantity to replace all of the common-isotope oxygen that was removed.

Dual redox catalysts for oxygen reduction and evolution reactions: towards a redox flow Li-O2 battery.

PubMed

Zhu, Yun Guang; Jia, Chuankun; Yang, Jing; Pan, Feng; Huang, Qizhao; Wang, Qing

2015-06-11

A redox flow lithium-oxygen battery (RFLOB) by using soluble redox catalysts with good performance was demonstrated for large-scale energy storage. The new device enables the reversible formation and decomposition of Li2O2 via redox targeting reactions in a gas diffusion tank, spatially separated from the electrode, which obviates the passivation and pore clogging of the cathode.

Investigation of the Effects of Biodiesel-based Na on Emissions Control Components

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

Brookshear, D. William; Nguyen, Ke; Toops, Todd J

2012-01-01

A single-cylinder diesel engine was used to investigate the impact of biodiesel-based Na on emissions control components using specially blended 20% biodiesel fuel (B20). The emissions control components investigated were a diesel oxidation catalyst (DOC), a Cu-zeolite-based NH{sub 3}-SCR (selective catalytic reduction) catalyst, and a diesel particulate filter (DPF). Both light-duty vehicle, DOC-SCR-DPF, and heavy-duty vehicle, DOC-DPF-SCR, emissions control configurations were employed. The accelerated Na aging is achieved by introducing elevated Na levels in the fuel, to represent full useful life exposure, and periodically increasing the exhaust temperature to replicate DPF regeneration. To assess the validity of the implemented acceleratedmore » Na aging protocol, engine-aged lean NO{sub x} traps (LNTs), DOCs and DPFs are also evaluated. To fully characterize the impact on the catalytic activity the LNT, DOC and SCR catalysts were evaluated using a bench flow reactor. The evaluation of the aged DOC samples and LNT show little to no deactivation as a result of Na contamination. However, the SCR in the light-duty configuration (DOC-SCR-DPF) was severely affected by Na contamination, especially when NO was the only fed NO{sub x} source. In the heavy-duty configuration (DOC-DPF-SCR), no impact is observed in the SCR NO{sub x} reduction activity. Electron probe micro-analysis (EPMA) reveals that Na contamination on the LNT, DOC, and SCR samples is present throughout the length of the catalysts with a higher concentration on the washcoat surface. In both the long-term engine-aged DPF and the accelerated Na-aged DPFs, there is significant Na ash present in the upstream channels; however, in the engine-aged sample lube oil-based ash is the predominant constituent.« less

Hybrid photocathodes for solar fuel production: coupling molecular fuel-production catalysts with solid-state light harvesting and conversion technologies.

PubMed

Cedeno, Diana; Krawicz, Alexandra; Moore, Gary F

2015-06-06

Artificial photosynthesis is described as the great scientific and moral challenge of our time. We imagine a future where a significant portion of our energy is supplied by such technologies. However, many scientific, engineering and policy challenges must be addressed for this realization. Scientific challenges include the development of effective strategies to couple light absorption, electron transfer and catalysis for efficient conversion of light energy to chemical energy as well as the construction and study of structurally diverse assemblies to carry out these processes. In this article, we review recent efforts from our own research to develop a modular approach to interfacing molecular fuel-production catalysts to visible-light-absorbing semiconductors and discuss the role of the interfacing material as a protection layer for the catalysts as well as the underpinning semiconductor. In concluding, we briefly discuss the potential benefits of a globally coordinated project on artificial photosynthesis that interfaces teams of scientists, engineers and policymakers. Further, we offer cautions that such a large interconnected organization should consider. This article is inspired by, and draws largely from, an invited presentation given by the corresponding author at the Royal Society at Chicheley Hall, home of the Kavli Royal Society International Centre, Buckinghamshire on the themed meeting topic: 'Do we need a global project on artificial photosynthesis?'

Effect of the components' interface on the synthesis of methanol over Cu/ZnO from CO2/H2: a microkinetic analysis based on DFT + U calculations.

PubMed

Tang, Qian-Lin; Zou, Wen-Tian; Huang, Run-Kun; Wang, Qi; Duan, Xiao-Xuan

2015-03-21

The elucidation of chemical reactions occurring on composite systems (e.g., copper (Cu)/zincite (ZnO)) from first principles is a challenging task because of their very large sizes and complicated equilibrium geometries. By combining the density functional theory plus U (DFT + U) method with microkinetic modeling, the present study has investigated the role of the phase boundary in CO2 hydrogenation to methanol over Cu/ZnO. The absence of hydrogenation locations created by the interface between the two catalyst components was revealed based on the calculated turnover frequency under realistic conditions, in which the importance of interfacial copper to provide spillover hydrogen for remote Cu(111) sites was stressed. Coupled with the fact that methanol production on the binary catalyst was recently believed to predominantly involve the bulk metallic surface, the spillover of interface hydrogen atoms onto Cu(111) facets facilitates the production process. The cooperative influence of the two different kinds of copper sites can be rationalized applying the Brönsted-Evans-Polanyi (BEP) relationship and allows us to find that the catalytic activity of ZnO-supported Cu catalysts is of volcano type with decrease in the particle size. Our results here may have useful implications in the future design of new Cu/ZnO-based materials for CO2 transformation to methanol.

Space shuttle on-orbit flight control software requirements, preliminary version

NASA Technical Reports Server (NTRS)

1975-01-01

Software modules associated with various flight control functions for the space shuttle orbiter are described. Data flow, interface requirements, initialization requirements and module sequencing requirements are considered. Block diagrams and tables are included.

Development of Augmented Spark Impinging Igniter System for Methane Engines

NASA Technical Reports Server (NTRS)

Marshall, William M.; Osborne, Robin J.; Greene, Sandra E.

2017-01-01

The Lunar Cargo Transportation and Landing by Soft Touchdown (Lunar CATALYST) program is establishing multiple no-funds-exchanged Space Act Agreement (SAA) partnerships with U.S. private sector entities. The purpose of this program is to encourage the development of robotic lunar landers that can be integrated with U.S. commercial launch capabilities to deliver payloads to the lunar surface. NASA can share technology and expertise under the SAA for the benefit of the CATALYST partners. MSFC seeking to vacuum test Augmented Spark Impinging (ASI) igniter with methane and new exciter units to support CATALYST partners and NASA programs. ASI has previously been used/tested successfully at sea-level, with both O2/CH4 and O2/H2 propellants. Conventional ignition exciter systems historically experienced corona discharge issues in vacuum. Often utilized purging or atmospheric sealing on high voltage lead to remedy. Compact systems developed since PCAD could eliminate the high-voltage lead and directly couple the exciter to the spark igniter. MSFC developed Augmented Spark Impinging (ASI) igniter. Successfully used in several sea-level test programs. Plasma-assisted design. Portion of ox flow is used to generate hot plasma. Impinging flows downstream of plasma. Additional fuel flow down torch tube sleeve for cooling near stoichiometric torch flame. Testing done at NASA GRC Altitude Combustion Stand (ACS) facility 2000-lbf class facility with altitude simulation up to around 100,000 ft. (0.2 psia [10 Torr]) via nitrogen driven ejectors. Propellant conditioning systems can provide temperature control of LOX/CH4 up to test article.

Experimental Studies of the Interaction Between a Parallel Shear Flow and a Directionally-Solidifying Front

NASA Technical Reports Server (NTRS)

Zhang, Meng; Maxworthy, Tony

1999-01-01

It has long been recognized that flow in the melt can have a profound influence on the dynamics of a solidifying interface and hence the quality of the solid material. In particular, flow affects the heat and mass transfer, and causes spatial and temporal variations in the flow and melt composition. This results in a crystal with nonuniform physical properties. Flow can be generated by buoyancy, expansion or contraction upon phase change, and thermo-soluto capillary effects. In general, these flows can not be avoided and can have an adverse effect on the stability of the crystal structures. This motivates crystal growth experiments in a microgravity environment, where buoyancy-driven convection is significantly suppressed. However, transient accelerations (g-jitter) caused by the acceleration of the spacecraft can affect the melt, while convection generated from the effects other than buoyancy remain important. Rather than bemoan the presence of convection as a source of interfacial instability, Hurle in the 1960s suggested that flow in the melt, either forced or natural convection, might be used to stabilize the interface. Delves considered the imposition of both a parabolic velocity profile and a Blasius boundary layer flow over the interface. He concluded that fast stirring could stabilize the interface to perturbations whose wave vector is in the direction of the fluid velocity. Forth and Wheeler considered the effect of the asymptotic suction boundary layer profile. They showed that the effect of the shear flow was to generate travelling waves parallel to the flow with a speed proportional to the Reynolds number. There have been few quantitative, experimental works reporting on the coupling effect of fluid flow and morphological instabilities. Huang studied plane Couette flow over cells and dendrites. It was found that this flow could greatly enhance the planar stability and even induce the cell-planar transition. A rotating impeller was buried inside the sample cell, driven by an outside rotating magnet, in order to generate the flow. However, it appears that this was not a well-controlled flow and may also have been unsteady. In the present experimental study, we want to study how a forced parallel shear flow in a Hele-Shaw cell interacts with the directionally solidifying crystal interface. The comparison of experimental data show that the parallel shear flow in a Hele-Shaw cell has a strong stabilizing effect on the planar interface by damping the existing initial perturbations. The flow also shows a stabilizing effect on the cellular interface by slightly reducing the exponential growth rate of cells. The left-right symmetry of cells is broken by the flow with cells tilting toward the incoming flow direction. The tilting angle increases with the velocity ratio. The experimental results are explained through the parallel flow effect on lateral solute transport. The phenomenon of cells tilting against the flow is consistent with the numerical result of Dantzig and Chao.

Nanoscale Catalysts for NMR Signal Enhancement by Reversible Exchange

PubMed Central

2015-01-01

Two types of nanoscale catalysts were created to explore NMR signal enhancement via reversible exchange (SABRE) at the interface between heterogeneous and homogeneous conditions. Nanoparticle and polymer comb variants were synthesized by covalently tethering Ir-based organometallic catalysts to support materials composed of TiO2/PMAA (poly(methacrylic acid)) and PVP (polyvinylpyridine), respectively, and characterized by AAS, NMR, and DLS. Following parahydrogen (pH2) gas delivery to mixtures containing one type of “nano-SABRE” catalyst particle, a target substrate, and ethanol, up to ∼(−)40-fold and ∼(−)7-fold 1H NMR signal enhancements were observed for pyridine substrates using the nanoparticle and polymer comb catalysts, respectively, following transfer to high field (9.4 T). These enhancements appear to result from intact particles and not from any catalyst molecules leaching from their supports; unlike the case with homogeneous SABRE catalysts, high-field (in situ) SABRE effects were generally not observed with the nanoscale catalysts. The potential for separation and reuse of such catalyst particles is also demonstrated. Taken together, these results support the potential utility of rational design at molecular, mesoscopic, and macroscopic/engineering levels for improving SABRE and HET-SABRE (heterogeneous-SABRE) for applications varying from fundamental studies of catalysis to biomedical imaging. PMID:26185545

Role of bonding mechanisms during transfer hydrogenation reaction on heterogeneous catalysts of platinum nanoparticles supported on zinc oxide nanorods

NASA Astrophysics Data System (ADS)

Al-Alawi, Reem A.; Laxman, Karthik; Dastgir, Sarim; Dutta, Joydeep

2016-07-01

For supported heterogeneous catalysis, the interface between a metal nanoparticle and the support plays an important role. In this work the dependency of the catalytic efficiency on the bonding chemistry of platinum nanoparticles supported on zinc oxide (ZnO) nanorods is studied. Platinum nanoparticles were deposited on ZnO nanorods (ZnO NR) using thermal and photochemical processes and the effects on the size, distribution, density and chemical state of the metal nanoparticles upon the catalytic activities are presented. The obtained results indicate that the bonding at Pt-ZnO interface depends on the deposition scheme which can be utilized to modulate the surface chemistry and thus the activity of the supported catalysts. Additionally, uniform distribution of metal on the catalyst support was observed to be more important than the loading density. It is also found that oxidized platinum Pt(IV) (platinum hydroxide) provided a more suitable surface for enhancing the transfer hydrogenation reaction of cyclohexanone with isopropanol compared to zero valent platinum. Photochemically synthesized ZnO supported nanocatalysts were efficient and potentially viable for upscaling to industrial applications.

Ionic Attachment as a Feasible Approach to Heterogenizing Anionic Solution Catalysts. The Carbonylation of Methanol,

DTIC Science & Technology

1980-08-01

carbonylation of methanol to acetic acid reaction is well suited for a demonstration of the feasibility and value of ionically binding a catalyst to a...approximate doubling of the reaction rate. This result suggests that a liquid flow system design in which there is a large catalyst to methanol ratio could...Heterogenizing Anionic Solution Catalysts . The Carbonylation of Methanol by Russell S. Drago, Eric D. Nyberg, Anton El A’mma and Alan Zombeck ABSTRACT -’Few

Design of an FPGA-based electronic flow regulator (EFR) for spacecraft propulsion system

NASA Astrophysics Data System (ADS)

Manikandan, J.; Jayaraman, M.; Jayachandran, M.

2011-02-01

This paper describes a scheme for electronically regulating the flow of propellant to the thruster from a high-pressure storage tank used in spacecraft application. Precise flow delivery of propellant to thrusters ensures propulsion system operation at best efficiency by maximizing the propellant and power utilization for the mission. The proposed field programmable gate array (FPGA) based electronic flow regulator (EFR) is used to ensure precise flow of propellant to the thrusters from a high-pressure storage tank used in spacecraft application. This paper presents hardware and software design of electronic flow regulator and implementation of the regulation logic onto an FPGA.Motivation for proposed FPGA-based electronic flow regulation is on the disadvantages of conventional approach of using analog circuits. Digital flow regulation overcomes the analog equivalent as digital circuits are highly flexible, are not much affected due to noise, accurate performance is repeatable, interface is easier to computers, storing facilities are possible and finally failure rate of digital circuits is less. FPGA has certain advantages over ASIC and microprocessor/micro-controller that motivated us to opt for FPGA-based electronic flow regulator. Also the control algorithm being software, it is well modifiable without changing the hardware. This scheme is simple enough to adopt for a wide range of applications, where the flow is to be regulated for efficient operation.The proposed scheme is based on a space-qualified re-configurable field programmable gate arrays (FPGA) and hybrid micro circuit (HMC). A graphical user interface (GUI) based application software is also developed for debugging, monitoring and controlling the electronic flow regulator from PC COM port.

Tuning-free controller to accurately regulate flow rates in a microfluidic network

NASA Astrophysics Data System (ADS)

Heo, Young Jin; Kang, Junsu; Kim, Min Jun; Chung, Wan Kyun

2016-03-01

We describe a control algorithm that can improve accuracy and stability of flow regulation in a microfluidic network that uses a conventional pressure pump system. The algorithm enables simultaneous and independent control of fluid flows in multiple micro-channels of a microfluidic network, but does not require any model parameters or tuning process. We investigate robustness and optimality of the proposed control algorithm and those are verified by simulations and experiments. In addition, the control algorithm is compared with a conventional PID controller to show that the proposed control algorithm resolves critical problems induced by the PID control. The capability of the control algorithm can be used not only in high-precision flow regulation in the presence of disturbance, but in some useful functions for lab-on-a-chip devices such as regulation of volumetric flow rate, interface position control of two laminar flows, valveless flow switching, droplet generation and particle manipulation. We demonstrate those functions and also suggest further potential biological applications which can be accomplished by the proposed control framework.

Tuning-free controller to accurately regulate flow rates in a microfluidic network

PubMed Central

Heo, Young Jin; Kang, Junsu; Kim, Min Jun; Chung, Wan Kyun

2016-01-01

We describe a control algorithm that can improve accuracy and stability of flow regulation in a microfluidic network that uses a conventional pressure pump system. The algorithm enables simultaneous and independent control of fluid flows in multiple micro-channels of a microfluidic network, but does not require any model parameters or tuning process. We investigate robustness and optimality of the proposed control algorithm and those are verified by simulations and experiments. In addition, the control algorithm is compared with a conventional PID controller to show that the proposed control algorithm resolves critical problems induced by the PID control. The capability of the control algorithm can be used not only in high-precision flow regulation in the presence of disturbance, but in some useful functions for lab-on-a-chip devices such as regulation of volumetric flow rate, interface position control of two laminar flows, valveless flow switching, droplet generation and particle manipulation. We demonstrate those functions and also suggest further potential biological applications which can be accomplished by the proposed control framework. PMID:26987587

Gender and the Work-Family Interface: Exploring Differences across the Family Life Course

ERIC Educational Resources Information Center

Martinengo, Giuseppe; Jacob, Jenet I.; Hill, E. Jeffrey

2010-01-01

This study examines gender differences in the work-family interface across six family life stages using a global sample of IBM employees in 79 countries (N = 41,813). Family life stage was constructed using the age of respondent and age of youngest child. Results revealed that having young children at home was the critical catalyst for gender…

Processing eutectics in space

NASA Technical Reports Server (NTRS)

Douglas, F. C.; Galasso, F. S.

1974-01-01

Experimental work is reported which was directed toward obtaining interface shape control while a numerical thermal analysis program was being made operational. An experimental system was developed in which the solid-liquid interface in a directionally solidified aluminum-nickel eutectic could be made either concave to the melt or convex to the melt. This experimental system provides control over the solid-liquid interface shape and can be used to study the effect of such control on the microstructure. The SINDA thermal analysis program, obtained from Marshall Space Flight Center, was used to evaluate experimental directional solidification systems for the aluminum-nickel and the aluminum-copper eutectics. This program was applied to a three-dimensional ingot, and was used to calculate the thermal profiles in axisymmetric heat flow. The results show that solid-liquid interface shape control can be attained with physically realizable thermal configurations and the magnitudes of the required thermal inputs were indicated.

Interface Si donor control to improve dynamic performance of AlGaN/GaN MIS-HEMTs

NASA Astrophysics Data System (ADS)

Song, Liang; Fu, Kai; Zhang, Zhili; Sun, Shichuang; Li, Weiyi; Yu, Guohao; Hao, Ronghui; Fan, Yaming; Shi, Wenhua; Cai, Yong; Zhang, Baoshun

2017-12-01

In this letter, we have studied the performance of AlGaN/GaN metal-insulator-semiconductor high electron mobility transistors (MIS-HEMTs) with different interface Si donor incorporation which is tuned during the deposition process of LPCVD-SiNx which is adopted as gate dielectric and passivation layer. Current collapse of the MIS-HEMTs without field plate is suppressed more effectively by increasing the SiH2Cl2/NH3 flow ratio and the normalized dynamic on-resistance (RON) is reduced two orders magnitude after off-state VDS stress of 600 V for 10 ms. Through interface characterization, we have found that the interface deep-level traps distribution with high Si donor incorporation by increasing the SiH2Cl2/NH3 flow ratio is lowered. It's indicated that the Si donors are most likely to fill and screen the deep-level traps at the interface resulting in the suppression of slow trapping process and the virtual gate effect. Although the Si donor incorporation brings about the increase of gate leakage current (IGS), no clear degradation of breakdown voltage can be seen by choosing appropriate SiH2Cl2/NH3 flow ratio.

Effect of a surface tension gradient on the slip flow along a superhydrophobic air-water interface

NASA Astrophysics Data System (ADS)

Song, Dong; Song, Baowei; Hu, Haibao; Du, Xiaosong; Du, Peng; Choi, Chang-Hwan; Rothstein, Jonathan P.

2018-03-01

Superhydrophobic surfaces have been shown to produce significant drag reduction in both laminar and turbulent flows by introducing an apparent slip velocity along an air-water interface trapped within the surface roughness. In the experiments presented within this study, we demonstrate the existence of a surface tension gradient associated with the resultant Marangoni flow along an air-water interface that causes the slip velocity and slip length to be significantly reduced. In this study, the slip velocity along a millimeter-sized air-water interface was investigated experimentally. This large-scale air-water interface facilitated a detailed investigation of the interfacial velocity profiles as the flow rate, interfacial curvature, and interface geometry were varied. For the air-water interfaces supported above continuous grooves (concentric rings within a torsional shear flow) where no surface tension gradient exists, a slip velocity as high as 30% of the bulk velocity was observed. However, for the air-water interfaces supported above discontinuous grooves (rectangular channels in a Poiseuille flow), the presence of a surface tension gradient reduced the slip velocity and in some cases resulted in an interfacial velocity that was opposite to the main flow direction. The curvature of the air-water interface in the spanwise direction was found to dictate the details of the interfacial flow profile with reverse flow in the center of the interface for concave surfaces and along the outside of the interface for convex surfaces. The deflection of the air-water interface was also found to greatly affect the magnitude of the slip. Numerical simulations imposed with a relatively small surface tension gradient along the air-water interface were able to predict both the reduced slip velocity and back flow along the air-water interface.

Method of performing sugar dehydration and catalyst treatment

DOEpatents

Hu, Jianli [Kennewick, WA; Holladay, Johnathan E [Kennewick, WA; Zhang, Xinjie [Burlington, MA; Wang, Yong [Richland, WA

2010-06-01

The invention includes a method of treating a solid acid catalyst. After exposing the catalyst to a mixture containing a sugar alcohol, the catalyst is washed with an organic solvent and is then exposed to a second reaction mixture. The invention includes a process for production of anhydrosugar alcohol. A solid acid catalyst is provided to convert sugar alcohol in a first sample to an anhydrosugar alcohol. The catalyst is then washed with an organic solvent and is subsequently utilized to expose a second sample. The invention includes a method for selective production of an anhydrosugar. A solid acid catalyst is provided within a reactor and anhydrosugar alcohol is formed by flowing a starting sugar alcohol into the reactor. The acid catalyst is then exposed to an organic solvent which allows a greater amount of additional anhydrosugar to be produced than would occur without exposing the acid catalyst to the organic solvent.

Movement of the saltwater interface in the surficial aquifer system in response to hydrologic stresses and water-management practices, Broward County, Florida

USGS Publications Warehouse

Dausman, Alyssa M.; Langevin, Christian D.

2005-01-01

A study was conducted to evaluate the relation between water-level fluctuations and saltwater intrusion in Broward County, Florida. The objective was achieved through data collection at selected wells in Broward County and through the development of a variable-density ground-water flow model. The numerical model is representative of many locations in Broward County that contain a well field, control structure, canal, the Intracoastal Waterway, and the Atlantic Ocean. The model was used to simulate short-term movement (from tidal fluctuations to monthly changes) and long-term movement (greater than 10 years) of the saltwater interface resulting from changes in rainfall, well-field withdrawals, sea-level rise, and upstream canal stage. The SEAWAT code, which is a combined version of the computer codes, MODFLOW and MT3D, was used to simulate the complex variable-density flow patterns. Model results indicated that the canal, control structure, and sea level have major effects on ground-water flow. For periods greater than 10 years, the upstream canal stage controls the movement and location of the saltwater interface. If upstream canal stage is decreased by 1 foot (0.3048 meter), the saltwater interface takes 50 years to move inland and stabilize. If the upstream canal stage is then increased by 1 foot (0.3048 meter), the saltwater interface takes 90 years to move seaward and stabilize. If sea level rises about 48 centimeters over the next 100 year as predicted, then inland movement of the saltwater interface may cause well-field contamination. For periods less than 10 years, simulation results indicated that a 3-year drought with increased well-field withdrawals probably will not have long-term effects on the position of the saltwater interface in the Biscayne aquifer. The saltwater interface returns to its original position in less than 10 years. Model results, however, indicated that the interface location in the lower part of the surficial aquifer system takes longer than 10 years to recover from a drought. Additionally, rainfall seems to have the greatest effect on saltwater interface movement in areas some distance from canals, but the upstream canal stage has the greatest effect on the movement of the saltwater interface near canals. Field data indicated that saltwater interface movement includes short-term fluctuations caused by tidal fluctuations and long-term seasonal fluctuations. Statistical analyses of daily-averaged data indicated that the saltwater interface moves in response to pumpage, rainfall, and upstream canal stage. In areas near the canal, the saltwater interface is most affected by canal stage because water-management structures control the stage in the upstream part of the canal and allow movement of the saltwater interface. In areas away from the canal, the saltwater interface is most affected by pumpage and rainfall, depending on the location of well fields. Data analyses also revealed that rainfall changes the vertical flow direction in the Biscayne aquifer. Results from the study indicated that upstream canal stage substantially affects the long-term position of the saltwater interface in the surficial aquifer system. The saltwater interface moves faster inland than seaward because of changes in upstream canal stage. For short-term problems, such as drought, the threat of saltwater intrusion in the Biscayne aquifer does not appear to be severe if the well-field withdrawal is increased; however, this conclusion is based on the assumption that well-field withdrawals will decrease once the drought is over. Sea-level rise may be a potential threat to the water supply in Broward County as the saltwater interface moves inland toward well fields.

Catalytic dehydration of ethanol using transition metal oxide catalysts.

PubMed

Zaki, T

2005-04-15

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

Oxyhydrochlorination catalyst

DOEpatents

Taylor, Charles E.; Noceti, Richard P.

1992-01-01

An improved catalyst and method for the oxyhydrochlorination of methane is disclosed. The catalyst includes a pyrogenic porous support on which is layered as active material, cobalt chloride in major proportion, and minor proportions of an alkali metal chloride and of a rare earth chloride. On contact of the catalyst with a gas flow of methane, HCl and oxygen, more than 60% of the methane is converted and of that converted more than 40% occurs as monochloromethane. Advantageously, the monochloromethane can be used to produce gasoline boiling range hydrocarbons with the recycle of HCl for further reaction. This catalyst is also of value for the production of formic acid as are analogous catalysts with lead, silver or nickel chlorides substituted for the cobalt chloride.

Catalysis Science Initiative: Catalyst Design by Discovery Informatics

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

Delgass, William Nicholas; Abu-Omar, Mahdi; Caruthers, James

Catalysts selectively enhance the rates of chemical reactions toward desired products. Such reactions provide great benefit to society in major commercial sectors such as energy production, protecting the environment, and polymer products and thereby contribute heavily to the country’s gross national product. Our premise is that the level of fundamental understanding of catalytic events at the atomic and molecular scale has reached the point that more predictive methods can be developed to shorten the cycle time to new processes. The field of catalysis can be divided into two regimes: heterogeneous and homogeneous. For the heterogeneous catalysis regime, we have usedmore » the water-gas shift (WGS) reaction (CO + H2O + CO2 + H2O) over supported metals as a test bed. Detailed analysis and strong coupling of theory with experiment have led to the following conclusions: • The sequence of elementary steps goes through a COOH intermediate • The CO binding energy is a strong function of coverage of CO adsorbed on the surface in many systems • In the case of Au catalysts, the CO adsorption is generally too weak on surface with close atomic packing, but the enhanced binding at corner atoms (which are missing bonding partners) of cubo-octahedral nanoparticles increases the energy to a near optimal value and produces very active catalysts. • Reaction on the metal alone cannot account for the experimental results. The reaction is dual functional with water activation occurring at the metal-support interface. It is clear from our work that the theory component is essential, not only for prediction of new systems, but also for reconciling data and testing hypotheses regarding potential descriptors. Particularly important is the finding that the interface between nano-sized metal particles and the oxides that are used to support them represent a new state of matter in the sense that the interfacial bonding perturbs the chemical state of both metals atoms and the support atoms in the interfacial region. Some of the first theoretical descriptions of this important chemistry and potential new source of control of catalyst properties are be in preparation for submission. On the homogeneous catalysis side, we have used single site olefin polymerization as the testbed. This system is important because changes in a single ligand bonded to the catalytically active metal site can alter the rates of individual steps in the polymerization sequence and thereby change the properties of the resulting polymer, potentially improving its value in a hundred million pound per year industry. We have made a major advance in understanding such systems by developing a population balance kinetic model that allows us to predict the molecular weight distribution (MWD) of the product. That, in turn, allows use of MWD data to fit kinetic parameters. By combining monomer loss data, MWD, measurement of the number of working active sites, and polymer end group analysis, we have a rich data set that is highly discriminating of kinetic mechanism. Thus, we have a robust tool for producing high quality, detailed kinetic parameters, which we have used to refine mechanisms presented in the literature and discover relationships between steric and electronic properties of group IV catalysts and individual rate constants in a number of systems. Our recent work on six-coordinate Zr, Ti, and Hf amine bis(phenolate) systems, we have shown that: • The sterics (bulkiness) of the ligands specifically affect the chain termination reaction • The electron density on the metal controls misinsertion (flipped orientation) of the olefin into the growing polymer • Steric effects related to the size of the ortho ligand on the catalyst have been shown to strongly affect its the degree of dormancy, i.e. tendency to stop reacting • Changes in the size of the amine pendent group on the catalyst can have such a strong effect on chain termination as to change the catalyst from one that produces only oligomers to one that incorporates oligomers in polymer chains to introduce chain branching. These effects control the length of molecular chains, the number of errors in the regularity of the chains, and the variation of chain lengths in the final product distribution. These characteristics, in turn, determine the properties of the resulting polymer material. Predictive modeling of polymerization process cannot be done without the quantitative rate constant determination that our unique and comprehensive approach has produced. This tool, combined with insights on how catalyst chemistry affects the rate constants, is an important step toward establishing the quantitative relationships between catalyst chemistry and polymer properties that will allow more efficient searches for new catalysts and speed the discovery process. Thus, in both the heterogeneous and homogeneous catalysis areas, this work has brought important new understanding to the field. The technical effectiveness of our approach is demonstrated by its success. For heterogeneous catalysis, experimental work alone showed the important of the metal-support interface, but the integration with theory has allowed deeper understanding of the fundamental source of the effects and shown the path for how to use this understanding for discovery. In the case of homogeneous catalysis, methodology for determination of which reactions are needed to account for the data and the extraction of quantitative values for rate constants for those reactions allows accurate modeling of reaction behavior. This allowed correlation of trends in catalyst properties with alterations of specific rates, thus contributing to a data base that will guide catalyst discovery. While not yet realized, the economic benefits of this approach will come in significantly shortened cycle times for discovery and ability to fill product demand at lower price.« less

Catalytic ignition of hydrogen/oxygen

NASA Technical Reports Server (NTRS)

Green, James M.; Zurawski, Robert L.

1988-01-01

An experimental program was conducted to evaluate the catalytic ignition of gaseous hydrogen and oxygen. Shell 405 granular catalyst and a unique monolithic sponge catalyst were tested. Mixture ratio, mass flow rate, propellant inlet temperature, and back pressure were varied parametrically in testing to determine the operational limits of a catalytic igniter. The test results showed that the gaseous hydrogen/oxygen propellant combination can be ignited catalytically using Shell 405 catalyst over a wide range of mixture ratios, mass flow rates, and propellant injection temperatures. These operating conditions must be optimized to ensure reliable ignition for an extended period of time. The results of the experimental program and the established operational limits for a catalytic igniter using both the granular and monolithic catalysts are presented. The capabilities of a facility constructed to conduct the igniter testing and the advantages of a catalytic igniter over other ignition systems for gaseous hydrogen and oxygen are also discussed.

Continuous Flow Aerobic Alcohol Oxidation Reactions Using a Heterogeneous Ru(OH)x/Al2O3 Catalyst

PubMed Central

2015-01-01

Ru(OH)x/Al2O3 is among the more versatile catalysts for aerobic alcohol oxidation and dehydrogenation of nitrogen heterocycles. Here, we describe the translation of batch reactions to a continuous-flow method that enables high steady-state conversion and single-pass yields in the oxidation of benzylic alcohols and dehydrogenation of indoline. A dilute source of O2 (8% in N2) was used to ensure that the reaction mixture, which employs toluene as the solvent, is nonflammable throughout the process. A packed bed reactor was operated isothermally in an up-flow orientation, allowing good liquid–solid contact. Deactivation of the catalyst during the reaction was modeled empirically, and this model was used to achieve high conversion and yield during extended operation in the aerobic oxidation of 2-thiophene methanol (99+% continuous yield over 72 h). PMID:25620869

Transesterification of rapeseed oil for biodiesel production in trickle-bed reactors packed with heterogeneous Ca/Al composite oxide-based alkaline catalyst.

PubMed

Meng, Yong-Lu; Tian, Song-Jiang; Li, Shu-Fen; Wang, Bo-Yang; Zhang, Min-Hua

2013-05-01

A conventional trickle bed reactor and its modified type both packed with Ca/Al composite oxide-based alkaline catalysts were studied for biodiesel production by transesterification of rapeseed oil and methanol. The effects of the methanol usage and oil flow rate on the FAME yield were investigated under the normal pressure and methanol boiling state. The oil flow rate had a significant effect on the FAME yield for the both reactors. The modified trickle bed reactor kept over 94.5% FAME yield under 0.6 mL/min oil flow rate and 91 mL catalyst bed volume, showing a much higher conversion and operational stability than the conventional type. With the modified trickle bed reactor, both transesterification and methanol separation could be performed simultaneously, and glycerin and methyl esters were separated additionally by gravity separation. Copyright © 2013 Elsevier Ltd. All rights reserved.

In-Water and Neat Batch and Continuous-Flow Direct Esterification and Transesterification by a Porous Polymeric Acid Catalyst

PubMed Central

Baek, Heeyoel; Minakawa, Maki; Yamada, Yoichi M. A.; Han, Jin Wook; Uozumi, Yasuhiro

2016-01-01

A porous phenolsulphonic acid—formaldehyde resin (PAFR) was developed. The heterogeneous catalyst PAFR was applied to the esterification of carboxylic acids and alcohols, affording the carboxylic acid esters in a yield of up to 95% where water was not removed from the reaction mixture. Surprisingly, the esterification in water as a solvent proceeded to afford the desired esters in high yield. PAFR provided the corresponding esters in higher yield than other homogeneous and heterogeneous catalysts. The transesterification of alcohols and esters was also investigated by using PAFR, giving the corresponding esters. PAFR was applied to the batch-wise and continuous-flow production of biodiesel fuel FAME. The PAFR-packed flow reactor that was developed for the synthesis of carboxylic acids and FAME worked for four days without loss of its catalytic activity. PMID:27189631

Monomolecular Siloxane Film as a Model of Single Site Catalysts

DOE PAGES

Martynowycz, Michael W.; Hu, Bo; Kuzmenko, Ivan; ...

2016-09-06

Achieving structurally well-defined catalytic species requires a fundamental understanding of surface chemistry. Detailed structural characterization of the catalyst binding sites in situ, such as single site catalysts on silica supports, is technically challenging or even unattainable. Octadecyltrioxysilane (OTOS) monolayers formed from octadecyltrimethoxysilane (OTMS) at the air-liquid interface after hydrolysis and condensation at low pH were chosen as a model system of surface binding sites in silica-supported Zn 2+ catalysts. We characterize the system by grazing incidence X-ray diffraction, X-ray reflectivity (XR), and X-ray fluorescence spectroscopy (XFS). Previous X-ray and infrared surface studies of OTMS/OTOS films at the airliquid interface proposedmore » the formation of polymer OTOS structures. According to our analysis, polymer formation is inconsistent with the X-ray observations and structural properties of siloxanes; it is energetically unfavorable and thus highly unlikely. We suggest an alternative mechanism of hydrolysis/condensation in OTMS leading to the formation of structurally allowed cyclic trimers with the six-membered siloxane rings, which explain well both the X-ray and infrared results. XR and XFS consistently demonstrate that tetrahedral [Zn(NH 3) 4] 2+ ions bind to hydroxyl groups of the film at a stoichiometric ratio of OTOS:Zn ~ 2:1. The high binding affinity of zinc ions to OTOS trimers suggests that the six-membered siloxane rings are binding locations for single site Zn/SiO 2 catalysts. Finally, our results show that OTOS monolayers may serve as a platform for studying silica surface chemistry or hydroxyl-mediated reactions.« less

Manipulating the Rate-Limiting Step in Water Oxidation Catalysis by Ruthenium Bipyridine–Dicarboxylate Complexes

DOE PAGES

Shaffer, David W.; Xie, Yan; Szalda, David J.; ...

2016-11-01

In order to gain a deeper mechanistic understanding of water oxidation by [(bda)Ru(L) 2] catalysts (bdaH 2 = [2,2'-bipyridine]-6,6'-dicarboxylic acid; L = pyridine-type ligand), a series of modified catalysts with one and two trifluoromethyl groups in the 4 position of the bda 2– ligand was synthesized and studied using stopped-flow kinetics. The additional $-$CF 3 groups increased the oxidation potentials for the catalysts and enhanced the rate of electrocatalytic water oxidation at low pH. Stopped-flow measurements of cerium(IV)-driven water oxidation at pH 1 revealed two distinct kinetic regimes depending on catalyst concentration. At relatively high catalyst concentration (ca. ≥10 –4more » M), the rate-determining step (RDS) was a proton-coupled oxidation of the catalyst by cerium(IV) with direct kinetic isotope effects (KIE > 1). At low catalyst concentration (ca. ≤10 –6 M), the RDS was a bimolecular step with k H/k D ≈ 0.8. The results support a catalytic mechanism involving coupling of two catalyst molecules. The rate constants for both RDSs were determined for all six catalysts studied. The presence of $-$CF 3 groups had inverse effects on the two steps, with the oxidation step being fastest for the unsubstituted complexes and the bimolecular step being faster for the most electron-deficient complexes. Finally, though the axial ligands studied here did not significantly affect the oxidation potentials of the catalysts, the nature of the ligand was found to be important not only in the bimolecular step but also in facilitating electron transfer from the metal center to the sacrificial oxidant.« less

Development of a prototype two-phase thermal bus system for Space Station

NASA Technical Reports Server (NTRS)

Myron, D. L.; Parish, R. C.

1987-01-01

This paper describes the basic elements of a pumped two-phase ammonia thermal control system designed for microgravity environments, the development of the concept into a Space Station flight design, and design details of the prototype to be ground-tested in the Johnson Space Center (JSC) Thermal Test Bed. The basic system concept is one of forced-flow heat transport through interface heat exchangers with anhydrous ammonia being pumped by a device expressly designed for two-phase fluid management in reduced gravity. Control of saturation conditions, and thus system interface temperatures, is accomplished with a single central pressure regulating valve. Flow control and liquid inventory are controlled by passive, nonelectromechanical devices. Use of these simple control elements results in minimal computer controls and high system reliability. Building on the basic system concept, a brief overview of a potential Space Station flight design is given. Primary verification of the system concept will involve testing at JSC of a 25-kW ground test article currently in fabrication.

Magic angle spinning nuclear magnetic resonance apparatus and process for high-resolution in situ investigations

DOEpatents

Hu, Jian Zhi; Sears, Jr., Jesse A.; Hoyt, David W.; Mehta, Hardeep S.; Peden, Charles H. F.

2015-11-24

A continuous-flow (CF) magic angle sample spinning (CF-MAS) NMR rotor and probe are described for investigating reaction dynamics, stable intermediates/transition states, and mechanisms of catalytic reactions in situ. The rotor includes a sample chamber of a flow-through design with a large sample volume that delivers a flow of reactants through a catalyst bed contained within the sample cell allowing in-situ investigations of reactants and products. Flow through the sample chamber improves diffusion of reactants and products through the catalyst. The large volume of the sample chamber enhances sensitivity permitting in situ .sup.13C CF-MAS studies at natural abundance.

Fischer-Tropsch synthesis from a low H/sub 2/:CO gas in a dry fluidized-bed system. Volume 2. Development of microreactor systems for unsteady-state Fischer-Tropsch synthesis. Final technical report. [408 references

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

Whiting, G.K.; Liu, Y.A.; Squires, A.M.

1986-10-01

Vibrofluidized microreactor systems have been developed for studies of unsteady-state Fischer-Tropsch synthesis. This development is aimed at preventing carbon deposition on a fused-iron catalyst in a novel reactor called the ''heat tray.'' This reactor involves a supernatant gas flowing over a shallow fluidized bed of catalyst particles. Three systems were built: (1) a vibrofluidized-bed microreactor system for obtaining baseline carbon deposition information under industrially important reaction conditions; (2) a sliding-plug vibrofluidized-bed microreactor system for rapid switching of feed gases in the F-T synthesis; and (3) a cold-flow microreactor model for studying the gas mixing characteristics of the sliding-plug vibrofluidized-bed microreactor.more » The results show that catalyst defluidization occurred under steady-state synthesis conditions below 395 C using a feed gas of H/sub 2//CO ratio of 2:1 or less. Above 395 C, the probability of hydrocarbon chain growth (..cap alpha.. < 0.50 to prevent accumulation of high-molecular-weight species that cause defluidization. Carbon deposition was rapid above 395 C when a feed gas of H/sub 2//CO ratio of 2:1 or less was used. Cold-flow microreactor model studies show that rapid (on the order of seconds), quantitative switching of feed gases over a vibrofluidized bed of catalyst could be achieved. Vibrofluidization of the catalyst bed induced little backmixing of feed gas over the investigated flow-rate range of 417 to 1650 actual mm/sup 3//s. Further, cold-flow microreactor model studies showed intense solid mixing when a bed of fused-iron catalyst (150 to 300 microns) was vibrofluidized at 24 cycles per second with a peak-to-peak amplitude of 4 mm. The development of the microreactor systems provided an easy way of accurately determining integral fluid-bed kinetics in a laboratory reactor. 408 refs., 156 figs., 27 tabs.« less

Disruption of an Aligned Dendritic Network by Bubbles During Re-Melting in a Microgravity Environment

NASA Technical Reports Server (NTRS)

Grugel, Richard N.; Brush, Lucien N.; Anilkumar, Amrutur V.

2012-01-01

The quiescent Microgravity environment can be quite dynamic. Thermocapillary flow about "large" static bubbles on the order of 1mm in diameter was easily observed by following smaller tracer bubbles. The bubble induced flow was seen to disrupt a large dendritic array, effectively distributing free branches about the solid-liquid interface. "Small" dynamic bubbles were observed to travel at fast velocities through the mushy zone with the implication of bringing/detaching/redistributing dendrite arm fragments at the solid-liquid interface. Large and small bubbles effectively re-orient/re-distribute dendrite branches/arms/fragments at the solid liquid interface. Subsequent initiation of controlled directional solidification results in growth of dendrites having random orientations which significantly compromises the desired science.

Engineering the Activity and Lifetime of Heterogeneous Catalysts for Carbon Nanotube Growth via Substrate Ion Beam Bombardment (Postprint)

DTIC Science & Technology

2014-07-31

growth. Annealing of the catalyst film in an H2 ambient induces dewetting and leads to the formation of iron nanoparticles on top of the engineered...flow) at 585 °C for 10 min to dewet the catalyst layer into discrete nanoparticles. The samples were then rapidly cooled down to room temperature in a

Design and Implementation of Automatic Air Flow Rate Control System

NASA Astrophysics Data System (ADS)

Akbar, A.; Saputra, C.; Munir, M. M.; Khairurrijal

2016-08-01

Venturimeter is an apparatus that can be used to measure the air flow rate. In this experiment we designed a venturimeter which equipped with a valve that is used to control the air flow rate. The difference of pressure between the cross sections was measured with the differential pressure sensor GA 100-015WD which can calculate the difference of pressures from 0 to 3737.33 Pa. A 42M048C Z36 stepper motor was used to control the valve. The precision of this motor rotation is about 0.15 °. A Graphical User Interface (GUI) was developed to monitor and set the value of flow rate then an 8-bit microcontroller was used to process the control system In this experiment- the venturimeter has been examined to get the optimal parameter of controller. The results show that the controller can set the stable output air flow rate.

Synergistic effect of tungsten carbide and palladium on graphene for promoted ethanol electrooxidation.

PubMed

Yang, Jun; Xie, Ying; Wang, Ruihong; Jiang, Baojiang; Tian, Chungui; Mu, Guang; Yin, Jie; Wang, Bo; Fu, Honggang

2013-07-24

The synergistic effect of WC and Pd has large benefit for ethanol electrooxidation. The small-sized Pd nanoparticles (NPs) decorated tungsten carbide on graphene (Pd-WC/GN) will be a promising anode catalyst for the direct ethanol fuel cells. The density functional theory (DFT) calculations reveal that the strong interaction exists at the interface between Pd and WC, which induces the electron transfer from WC to Pd. Fortunately, the nanoscale architecture of Pd-WC/GN has been successfully fabricated in our experiments. X-ray photoelectron spectrum further confirms the existence of electron transfer from WC to Pd in a Pd-WC/GN nanohybrid. Notably, electrochemical tests show that the Pd-WC/GN catalyst exhibits low onset potential, a large electrochemical surface area, high activity, and stability for ethanol electrooxidation in alkaline solution compared with Pd/graphene and Pd/commercial Vulcan 72R carbon catalysts. The enhancement can be attributed to the synergistic effect of Pd and WC on graphene. At the interface between Pd and WC, the electron transfer from WC to Pd leads to the increased electron densities of surface Pd, which is available for weakening adsorption of intermediate oxygen-containing species such as CO and activating catalyst. Meanwhile, the increased tungsten oxide induced by electron transfer can facilitate the effective removal of intermediate species adsorbed on the Pd surface through a bifunctional mechanism or hydrogen spillover effect.

Fabrication and Characterization of New Composite Tio2 Carbon Nanofiber Anodic Catalyst Support for Direct Methanol Fuel Cell via Electrospinning Method

NASA Astrophysics Data System (ADS)

Abdullah, N.; Kamarudin, S. K.; Shyuan, L. K.; Karim, N. A.

2017-12-01

Platinum (Pt) is the common catalyst used in a direct methanol fuel cell (DMFC). However, Pt can lead towards catalyst poisoning by carbonaceous species, thus reduces the performance of DMFC. Thus, this study focuses on the fabrication of a new composite TiO2 carbon nanofiber anodic catalyst support for direct methanol fuel cells (DMFCs) via electrospinning technique. The distance between the tip and the collector (DTC) and the flow rate were examined as influencing parameters in the electrospinning technique. To ensure that the best catalytic material is fabricated, the nanofiber underwent several characterizations and electrochemical tests, including FTIR, XRD, FESEM, TEM, and cyclic voltammetry. The results show that D18, fabricated with a flow rate of 0.1 mLhr-1 and DTC of 18 cm, is an ultrafine nanofiber with the smallest average diameter, 136.73 ± 39.56 nm. It presented the highest catalyst activity and electrochemical active surface area value as 274.72 mAmg-1 and 226.75m2 g-1 PtRu, respectively, compared with the other samples.

Novel nano-semiconductor film layer supported nano-Pd Complex Nanostructured Catalyst Pd/Ⓕ-MeOx/AC for High Efficient Selective Hydrogenation of Phenol to Cyclohexanone.

PubMed

Si, Jiaqi; Ouyang, Wenbing; Zhang, Yanji; Xu, Wentao; Zhou, Jicheng

2017-04-28

Supported metal as a type of heterogeneous catalysts are the most widely used in industrial processes. High dispersion of the metal particles of supported catalyst is a key factor in determining the performance of such catalysts. Here we report a novel catalyst Pd/Ⓕ-MeO x /AC with complex nanostructured, Pd nanoparticles supported on the platelike nano-semiconductor film/activated carbon, prepared by the photocatalytic reduction method, which exhibited high efficient catalytic performance for selective hydrogenation of phenol to cyclohexanone. Conversion of phenol achieved up to more than 99% with a lower mole ratio (0.5%) of active components Pd and phenol within 2 h at 70 °C. The synergistic effect of metal nanoparticles and nano-semiconductors support layer and the greatly increasing of contact interface of nano-metal-semiconductors may be responsible for the high efficiency. This work provides a clear demonstration that complex nanostructured catalysts with nano-metal and nano-semiconductor film layer supported on high specific surface AC can yield enhanced catalytic activity and can afford promising approach for developing new supported catalyst.

Integrating Semiconducting Catalyst of ReS2 Nanosheets into P-silicon Photocathode toward Enhanced Solar Water Reduction.

PubMed

Zhao, Heng; Dai, Zhengyi; Xu, Xiaoyong; Pan, Jing; Hu, Jingguo

2018-06-22

Loading the electro-catalysts at the semiconductor-electrolyte interface is one of promising strategies to develop photoelectrochemical (PEC) water splitting cells. However, the assembly of compatible and synergistic heterojunction between the semiconductor and the selected catalyst remains challenging. Here, we report a hierarchical p-Si/ReS2 heterojunction photocathode fabricated through uniform growth vertically standing ReS2 nanosheets (NSs) on planar p-Si substrate for solar-driven hydrogen evolution reaction (HER). The laden ReS2 NSs not only serve as a high-activity HER catalyst but also render a suitable electronic band coupled with p-Si into a Ⅱ-type heterojunction, which facilitates the photo-induced charge production, separation and utilization. As a result, the assembled p-Si/ReS2 photocathode exhibits a 23-fold-increased photocurrent density at 0 VRHE and a 35-fold-enhanced photoconversion efficiency compared to pure p-Si counterpart. The bifunctional ReS2 as catalyst and semiconductor enables multi effects in improving light harvesting, charge separation and catalytic kinetics, highlighting the potential of semiconducting catalysts integrated into solar water splitting devices.

Operando characterization of catalysts through use of a portable microreactor

DOE PAGES

Zhao, Shen; Li, Yuanyuan; Stavitski, Eli; ...

2015-10-09

To provide new understandings of the mechanisms of catalytic reactions, improved methods are needed than can monitor changes in the electronic, structural and chemical properties of catalysts, doing so in the operando conditions in which catalysts work. We describe here a microreactor-based approach that integrates the capabilities of advanced x-ray, electron, optical and gas-phase compositional analysis techniques in operando conditions. For several exemplary catalytic systems, we demonstrate how this approach enables characterization of three major factors contributing to structure-property correlations evidenced in heterogeneously catalyzed reactions, namely: the atomic structure and elemental compositions of nanocatalysts; the physiochemical properties of the supportmore » and catalyst-support interfaces; and the gas and surface-phase chemistry occurring under operando conditions. We highlight the generality of the approach as well as outline opportunities for future developments.« less

Turbine blade with spar and shell

DOEpatents

Davies, Daniel O [Palm City, FL; Peterson, Ross H [Loxahatchee, FL

2012-04-24

A turbine blade with a spar and shell construction in which the spar and the shell are both secured within two platform halves. The spar and the shell each include outward extending ledges on the bottom ends that fit within grooves formed on the inner sides of the platform halves to secure the spar and the shell against radial movement when the two platform halves are joined. The shell is also secured to the spar by hooks extending from the shell that slide into grooves formed on the outer surface of the spar. The hooks form a serpentine flow cooling passage between the shell and the spar. The spar includes cooling holes on the lower end in the leading edge region to discharge cooling air supplied through the platform root and into the leading edge cooling channel.

Potential-sensing electrochemical atomic force microscopy for in operando analysis of water-splitting catalysts and interfaces

NASA Astrophysics Data System (ADS)

Nellist, Michael R.; Laskowski, Forrest A. L.; Qiu, Jingjing; Hajibabaei, Hamed; Sivula, Kevin; Hamann, Thomas W.; Boettcher, Shannon W.

2018-01-01

Heterogeneous electrochemical phenomena, such as (photo)electrochemical water splitting to generate hydrogen using semiconductors and/or electrocatalysts, are driven by the accumulated charge carriers and thus the interfacial electrochemical potential gradients that promote charge transfer. However, measurements of the "surface" electrochemical potential during operation are not generally possible using conventional electrochemical techniques, which measure/control the potential of a conducting electrode substrate. Here we show that the nanoscale conducting tip of an atomic force microscope cantilever can sense the surface electrochemical potential of electrocatalysts in operando. To demonstrate utility, we measure the potential-dependent and thickness-dependent electronic properties of cobalt (oxy)hydroxide phosphate (CoPi). We then show that CoPi, when deposited on illuminated haematite (α-Fe2O3) photoelectrodes, acts as both a hole collector and an oxygen evolution catalyst. We demonstrate the versatility of the technique by comparing surface potentials of CoPi-decorated planar and mesoporous haematite and discuss viability for broader application in the study of electrochemical phenomena.

Phase-field model of vapor-liquid-solid nanowire growth

NASA Astrophysics Data System (ADS)

Wang, Nan; Upmanyu, Moneesh; Karma, Alain

2018-03-01

We present a multiphase-field model to describe quantitatively nanowire growth by the vapor-liquid-solid (VLS) process. The free-energy functional of this model depends on three nonconserved order parameters that distinguish the vapor, liquid, and solid phases and describe the energetic properties of various interfaces, including arbitrary forms of anisotropic γ plots for the solid-vapor and solid-liquid interfaces. The evolution equations for those order parameters describe basic kinetic processes including the rapid (quasi-instantaneous) equilibration of the liquid catalyst to a droplet shape with constant mean curvature, the slow incorporation of growth atoms at the droplet surface, and crystallization within the droplet. The standard constraint that the sum of the phase fields equals unity and the conservation of the number of catalyst atoms, which relates the catalyst volume to the concentration of growth atoms inside the droplet, are handled via separate Lagrange multipliers. An analysis of the model is presented that rigorously maps the phase-field equations to a desired set of sharp-interface equations for the evolution of the phase boundaries under the constraint of force balance at three-phase junctions (triple points) given by the Young-Herring relation that includes torque term related to the anisotropy of the solid-liquid and solid-vapor interface excess free energies. Numerical examples of growth in two dimensions are presented for the simplest case of vanishing crystalline anisotropy and the more realistic case of a solid-liquid γ plot with cusped minima corresponding to two sets of (10 ) and (11 ) facets. The simulations reproduce many of the salient features of nanowire growth observed experimentally, including growth normal to the substrate with tapering of the side walls, transitions between different growth orientations, and crawling growth along the substrate. They also reproduce different observed relationships between the nanowire growth velocity and radius depending on the growth condition. For the basic normal growth mode, the steady-state solid-liquid interface tip shape consists of a main facet intersected by two truncated side facets ending at triple points. The ratio of truncated and main facet lengths are in quantitative agreement with the prediction of sharp-interface theory that is developed here for faceted nanowire growth in two dimensions.

Supported Ruthenium Catalysts for Sustainable Flow Chemistry

EPA Science Inventory

Continuous flow processes play a significant role in the process intensification of organic transformations, as is evident from the multitude of flow reactors that have been developed for various specific needs. These flow processes are deemed more sustainable due to the advantag...

Attrition and carbon formation on iron catalysts

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

Kohler, S.D.; Harrington, M.S.; Jackson, N.B.

1994-08-01

A serious engineering problem that needs to be addressed in the scale-up of slurry-phase, Fischer-Tropsch reactors is attrition of the precipitated iron catalyst. Attrition, which can break down the catalyst into particles too small to filter, results from both mechanical and chemical forces. This study examines the chemical causes of attrition in iron catalysts. A bench-scale, slurry-phase CSTR is used to simulate operating conditions that lead to attrition of the catalyst. The average particle size and size distribution of the catalyst samples are used to determine the effect of slurry temperature, reducing gas, gas flow rate and time upon attritionmore » of the catalyst. Carbon deposition, a possible contributing factor to attrition, has been examined using gravimetric analysis and TEM. Conditions affecting the rate of carbon deposition have been compared to those leading to attrition of the precipitated iron catalyst.« less

Carbon nanotubes on a substrate

DOEpatents

Gao, Yufei [Kennewick, WA; Liu, Jun [West Richland, WA

2002-03-26

The present invention includes carbon nanotubes whose hollow cores are 100% filled with conductive filler. The carbon nanotubes are in uniform arrays on a conductive substrate and are well-aligned and can be densely packed. The uniformity of the carbon nanotube arrays is indicated by the uniform length and diameter of the carbon nanotubes, both which vary from nanotube to nanotube on a given array by no more than about 5%. The alignment of the carbon nanotubes is indicated by the perpendicular growth of the nanotubes from the substrates which is achieved in part by the simultaneous growth of the conductive filler within the hollow core of the nanotube and the densely packed growth of the nanotubes. The present invention provides a densely packed carbon nanotube growth where each nanotube is in contact with at least one nearest-neighbor nanotube. The substrate is a conductive substrate coated with a growth catalyst, and the conductive filler can be single crystals of carbide formed by a solid state reaction between the substrate material and the growth catalyst. The present invention further provides a method for making the filled carbon nanotubes on the conductive substrates. The method includes the steps of depositing a growth catalyst onto the conductive substrate as a prepared substrate, creating a vacuum within a vessel which contains the prepared substrate, flowing H2/inert (e.g. Ar) gas within the vessel to increase and maintain the pressure within the vessel, increasing the temperature of the prepared substrate, and changing the H2/Ar gas to ethylene gas such that the ethylene gas flows within the vessel. Additionally, varying the density and separation of the catalyst particles on the conductive substrate can be used to control the diameter of the nanotubes.

Method of making carbon nanotubes on a substrate

DOEpatents

Gao, Yufei; Liu, Jun

2006-03-14

The present invention includes carbon nanotubes whose hollow cores are 100% filled with conductive filler. The carbon nanotubes are in uniform arrays on a conductive substrate and are well-aligned and can be densely packed. The uniformity of the carbon nanotube arrays is indicated by the uniform length and diameter of the carbon nanotubes, both which vary from nanotube to nanotube on a given array by no more than about 5%. The alignment of the carbon nanotubes is indicated by the perpendicular growth of the nanotubes from the substrates which is achieved in part by the simultaneous growth of the conductive filler within the hollow core of the nanotube and the densely packed growth of the nanotubes. The present invention provides a densely packed carbon nanotube growth where each nanotube is in contact with at least one nearest-neighbor nanotube. The substrate is a conductive substrate coated with a growth catalyst, and the conductive filler can be single crystals of carbide formed by a solid state reaction between the substrate material and the growth catalyst. The present invention further provides a method for making the filled carbon nanotubes on the conductive substrates. The method includes the steps of depositing a growth catalyst onto the conductive substrate as a prepared substrate, creating a vacuum within a vessel which contains the prepared substrate, flowing H2/inert (e.g. Ar) gas within the vessel to increase and maintain the pressure within the vessel, increasing the temperature of the prepared substrate, and changing the H2/Ar gas to ethylene gas such that the ethylene gas flows within the vessel. Additionally, varying the density and separation of the catalyst particles on the conductive substrate can be used to control the diameter of the nanotubes.

Catalytic recombination of dissociation products with Pt/SnO2 for rare and common isotope long-life, closed-cycle CO2 lasers

NASA Technical Reports Server (NTRS)

Brown, Kenneth G.; Sidney, B. D.; Schryer, D. R.; Upchurch, B. T.; Miller, I. M.

1986-01-01

This paper reports results on recombination of pulsed CO2 laser dissociation products with Pt/SnO2 catalysts, and supporting studies in a surrogate laboratory catalyst reactor. The closed-cycle, pulsed CO2 laser has been continuously operated for one million pulses with an overall power degradation of less than 5 percent by flowing the laser gas mixture through a 2-percent Pt/SnO2 catalyst bed. In the surrogate laboratory reactor, experiments have been conducted to determine isotopic exchange with the catalyst when using rare-isotope gases. The effects of catalyst pretreatment, sample weight, composition, and temperature on catalyst efficiency have also been determined.

An approach to tune the amplitude of surface ripple patterns

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

Kumar, Tanuj; Kanjilal, D.; Kumar, Ashish

An approach is presented to tune the amplitude of ripple patterns using ion beam. By varying the depth location of amorphous/crystalline interface, ripple patterns of different amplitude with similar wavelength were grown on the surface of Si (100) using 50 keV Ar{sup +} beam irradiation. Atomic force microscopy study demonstrates the tuning of amplitude of ripples patterns for wide range. Rutherford backscattering channeling measurement was performed to measure the depth location of amorphous/crystalline interface. It is postulated that the ion beam stimulated solid flow inside the amorphous layer controls the wavelength, whereas mass rearrangement at amorphous/crystalline interface controls the amplitude.

Photothermal Catalyst Engineering: Hydrogenation of Gaseous CO2 with High Activity and Tailored Selectivity

PubMed Central

Jia, Jia; Wang, Hong; Lu, Zhuole; O'Brien, Paul G.; Ghoussoub, Mireille; Duchesne, Paul; Zheng, Ziqi; Li, Peicheng; Qiao, Qiao; Wang, Lu; Gu, Alan; Jelle, Abdinoor A.; Dong, Yuchan; Wang, Qiang; Ghuman, Kulbir Kaur; Wood, Thomas; Qian, Chenxi; Shao, Yue; Qiu, Chenyue; Ye, Miaomiao; Zhu, Yimei; Lu, Zheng‐Hong; Zhang, Peng; Helmy, Amr S.; Singh, Chandra Veer; Kherani, Nazir P.; Perovic, Doug D.

2017-01-01

Abstract This study has designed and implemented a library of hetero‐nanostructured catalysts, denoted as Pd@Nb2O5, comprised of size‐controlled Pd nanocrystals interfaced with Nb2O5 nanorods. This study also demonstrates that the catalytic activity and selectivity of CO2 reduction to CO and CH4 products can be systematically tailored by varying the size of the Pd nanocrystals supported on the Nb2O5 nanorods. Using large Pd nanocrystals, this study achieves CO and CH4 production rates as high as 0.75 and 0.11 mol h−1 gPd −1, respectively. By contrast, using small Pd nanocrystals, a CO production rate surpassing 18.8 mol h−1 gPd −1 is observed with 99.5% CO selectivity. These performance metrics establish a new milestone in the champion league of catalytic nanomaterials that can enable solar‐powered gas‐phase heterogeneous CO2 reduction. The remarkable control over the catalytic performance of Pd@Nb2O5 is demonstrated to stem from a combination of photothermal, electronic and size effects, which is rationally tunable through nanochemistry. PMID:29051865

Elucidation of peptide sequence effects that control the activity, size, and function of nanoparticles

NASA Astrophysics Data System (ADS)

Coppage, Ryan

Bio-inspired nanoparticle catalysis offers the opportunity to improve on current catalytic standards with respect to turnover efficiency, organic solvent use, and thermal activation. Unfortunately, projected energy demands will soon outweigh our fuel supplies. The task of creating multifunctional catalysts that both lower thermal activation and possess a number of functions in aqueous conditions is daunting. Similar to these needs, nature has evolved to create a wide range of highly specialized catalytic processes, which incorporate inorganic materials, take place in ambient temperatures, and in an aqueous environment. These specialized biological systems provide inspiration, but are not applicable to current needs. Exploitation of these biotic-abiotic systems could allow for green, multifunctional catalysts. In the resulting works, a peptide sequence has been isolated via phage display with affinity for Pd surfaces, that forms stable, peptide-capped nanoparticles. Substitution of residues results in the tuning of both nanocatalyst activity and nanoparticle size, such that a peptide surface-controlling effect can be noted. These characteristics can be exploited to ultimately understand the binding interactions among bio-inorganic interfaces, such that a rational design of biomolecules can be realized for the synthesis of highly active, green, multifunctional nanomaterials.

Photothermal Catalyst Engineering: Hydrogenation of Gaseous CO 2 with High Activity and Tailored Selectivity

DOE PAGES

Jia, Jia; Wang, Hong; Lu, Zhuole; ...

2017-07-25

This study has designed and implemented a library of hetero-nanostructured catalysts, denoted as Pd@Nb 2O 5, comprised of size-controlled Pd nanocrystals interfaced with Nb 2O 5 nanorods. This study also demonstrates that the catalytic activity and selectivity of CO 2 reduction to CO and CH 4 products can be systematically tailored by varying the size of the Pd nanocrystals supported on the Nb 2O 5 nanorods. Using large Pd nanocrystals, this study achieves CO and CH 4 production rates as high as 0.75 and 0.11 mol h –1 gPd –1, respectively. By contrast, using small Pd nanocrystals, a CO productionmore » rate surpassing 18.8 mol h –1 gPd –1 is observed with 99.5% CO selectivity. These performance metrics establish a new milestone in the champion league of catalytic nanomaterials that can enable solar-powered gas-phase heterogeneous CO 2 reduction. In conclusion, the remarkable control over the catalytic performance of Pd@Nb 2O 5 is demonstrated to stem from a combination of photothermal, electronic and size effects, which is rationally tunable through nanochemistry.« less

Studies on dispersive stabilization of porous media flows

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

Daripa, Prabir, E-mail: prabir.daripa@math.tamu.edu; Gin, Craig

Motivated by a need to improve the performance of chemical enhanced oil recovery (EOR) processes, we investigate dispersive effects on the linear stability of three-layer porous media flow models of EOR for two different types of interfaces: permeable and impermeable interfaces. Results presented are relevant for the design of smarter interfaces in the available parameter space of capillary number, Peclet number, longitudinal and transverse dispersion, and the viscous profile of the middle layer. The stabilization capacity of each of these two interfaces is explored numerically and conditions for complete dispersive stabilization are identified for each of these two types ofmore » interfaces. Key results obtained are (i) three-layer porous media flows with permeable interfaces can be almost completely stabilized by diffusion if the optimal viscous profile is chosen, (ii) flows with impermeable interfaces can also be almost completely stabilized for short time, but become more unstable at later times because diffusion flattens out the basic viscous profile, (iii) diffusion stabilizes short waves more than long waves which leads to a “turning point” Peclet number at which short and long waves have the same growth rate, and (iv) mechanical dispersion further stabilizes flows with permeable interfaces but in some cases has a destabilizing effect for flows with impermeable interfaces, which is a surprising result. These results are then used to give a comparison of the two types of interfaces. It is found that for most values of the flow parameters, permeable interfaces suppress flow instability more than impermeable interfaces.« less

Energy and fuels from electrochemical interfaces

NASA Astrophysics Data System (ADS)

Stamenkovic, Vojislav R.; Strmcnik, Dusan; Lopes, Pietro P.; Markovic, Nenad M.

2017-01-01

Advances in electrocatalysis at solid-liquid interfaces are vital for driving the technological innovations that are needed to deliver reliable, affordable and environmentally friendly energy. Here, we highlight the key achievements in the development of new materials for efficient hydrogen and oxygen production in electrolysers and, in reverse, their use in fuel cells. A key issue addressed here is the degree to which the fundamental understanding of the synergy between covalent and non-covalent interactions can form the basis for any predictive ability in tailor-making real-world catalysts. Common descriptors such as the substrate-hydroxide binding energy and the interactions in the double layer between hydroxide-oxides and H---OH are found to control individual parts of the hydrogen and oxygen electrochemistry that govern the efficiency of water-based energy conversion and storage systems. Links between aqueous- and organic-based environments are also established, encouraging the 'fuel cell' and 'battery' communities to move forward together.

Efficient direct solar-to-hydrogen conversion by in situ interface transformation of a tandem structure

NASA Astrophysics Data System (ADS)

May, Matthias M.; Lewerenz, Hans-Joachim; Lackner, David; Dimroth, Frank; Hannappel, Thomas

2015-09-01

Photosynthesis is nature's route to convert intermittent solar irradiation into storable energy, while its use for an industrial energy supply is impaired by low efficiency. Artificial photosynthesis provides a promising alternative for efficient robust carbon-neutral renewable energy generation. The approach of direct hydrogen generation by photoelectrochemical water splitting utilizes customized tandem absorber structures to mimic the Z-scheme of natural photosynthesis. Here a combined chemical surface transformation of a tandem structure and catalyst deposition at ambient temperature yields photocurrents approaching the theoretical limit of the absorber and results in a solar-to-hydrogen efficiency of 14%. The potentiostatically assisted photoelectrode efficiency is 17%. Present benchmarks for integrated systems are clearly exceeded. Details of the in situ interface transformation, the electronic improvement and chemical passivation are presented. The surface functionalization procedure is widely applicable and can be precisely controlled, allowing further developments of high-efficiency robust hydrogen generators.

Efficient direct solar-to-hydrogen conversion by in situ interface transformation of a tandem structure

PubMed Central

May, Matthias M.; Lewerenz, Hans-Joachim; Lackner, David; Dimroth, Frank; Hannappel, Thomas

2015-01-01

Photosynthesis is nature's route to convert intermittent solar irradiation into storable energy, while its use for an industrial energy supply is impaired by low efficiency. Artificial photosynthesis provides a promising alternative for efficient robust carbon-neutral renewable energy generation. The approach of direct hydrogen generation by photoelectrochemical water splitting utilizes customized tandem absorber structures to mimic the Z-scheme of natural photosynthesis. Here a combined chemical surface transformation of a tandem structure and catalyst deposition at ambient temperature yields photocurrents approaching the theoretical limit of the absorber and results in a solar-to-hydrogen efficiency of 14%. The potentiostatically assisted photoelectrode efficiency is 17%. Present benchmarks for integrated systems are clearly exceeded. Details of the in situ interface transformation, the electronic improvement and chemical passivation are presented. The surface functionalization procedure is widely applicable and can be precisely controlled, allowing further developments of high-efficiency robust hydrogen generators. PMID:26369620

Stabilizing Wheels For Rover Vehicle

NASA Technical Reports Server (NTRS)

Collins, Earl R., Jr.

1990-01-01

Proposed articulated, normally-four-wheeled vehicle holds extra pair of wheels in reserve. Deployed to lengthen wheelbase on slopes, thereby making vehicle more stable, and to aid vehicle in negotiating ledge or to right vehicle if turned upside down. Extra wheels are drive wheels mounted on arms so they pivot on axis of forward drive wheels. Both extra wheels and arms driven by chains, hydraulic motors, or electric motors. Concept promises to make remotely controlled vehicles more stable and maneuverable in such applications as firefighting, handling hazardous materials, and carrying out operations in dangerous locations.

Operando Analyses of Solar Fuels Light Absorbers and Catalysts

DOE PAGES

Lewerenz, Hans -Joachim; Lichterman, Michael F.; Richter, Matthias H.; ...

2016-06-06

Operando synchrotron radiation photoelectron spectroscopy in the tender X-ray energy range has been used to obtain information on the energy-band relations of semiconductor and metal-covered semiconductor surfaces while in direct contact with aqueous electrolytes under potentiostatic control. The system that was investigated consists of highly doped Si substrates that were conformally coated with ~70 nm titania films produced by atomic-layer deposition. TiO 2/electrolyte and Si/TiO 2 /Ni/electrolyte interfaces were then analyzed by synchrotron radiation photoelectron spectroscopy. The PES data allows for determination of the flat-band position and identification of potential regions in which Fermi level pinning, depletion, or accumulation occurred. Operandomore » X-ray absorption spectroscopy (XAS) techniques were additionally used to investigate the properties of heterogeneous electrocatalysts for the oxygen-evolution reaction. Operando XAS including the pre-edge, edge and EXAFS regions allowed the development of a detailed picture of the catalysts under operating conditions, and elucidated the changes in the physical and electronic structure of the catalyst that accompanied increases in the applied potential. Specifically, XAS data, combined with DFT studies, indicated that the activity of the electrocatalyst correlated with the formation of Fe dopant sites in γ-NiOOH.« less

Polymer nanocomposite membranes with hierarchically structured catalysts for high throughput dehalogenation

NASA Astrophysics Data System (ADS)

Crock, Christopher A.

Halogenated organics are categorized as primary pollutants by the Environmental Protection Agency. Trichloroethylene (TCE), which had broad industrial use in the past, shows persistence in the environment because of its chemical stability. The large scale use and poor control of TCE resulted in its prolonged release into the environment before the carcinogenic risk associated with TCE was fully understood. TCE pollution stemmed from industrial effluents and improper disposal of solvent waste. Membrane reactors are promising technology for treating TCE polluted groundwater because of the high throughput, relatively low cost of membrane fabrication and facile retrofitting of existing membrane based water treatment facilities with catalytic membrane reactors. Compared to catalytic fluidized or fixed bed reactors, catalytic membrane reactors feature minimal diffusional limitation. Additionally, embedding catalyst within the membrane avoids the need for catalyst recovery and can prevent aggregation of catalytic nanoparticles. In this work, Pd/xGnP, Pd-Au/xGnP, and commercial Pd/Al2O3 nanoparticles were employed in batch and flow-through membrane reactors to catalyze the dehalogenation of TCE in the presence of dissolved H2. Bimetallic Pd-Au/xGnP catalysts were shown to be more active than monometallic Pd/xGnP or commercial Pd/Al 2O3 catalysts. In addition to synthesizing nanocomposite membranes for high-throughput TCE dehalogenation, the membrane based dehalogenation process was designed to minimize the detrimental impact of common catalyst poisons (S2-, HS-, and H2S -) by concurrent oxidation of sulfide species to gypsum in the presence of Ca2+ and removal of gypsum through membrane filtration. The engineered membrane dehalogenation process demonstrated that bimetallic Pd-Au/xGnP catalysts resisted deactivation by residual sulfide species after oxidation, and showed complete removal of gypsum during membrane filtration.

Impact of Fuel Metal Impurities on the Durability of a Light-Duty Diesel Aftertreatment System

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

Williams, A.; Burton, J.; McCormick, R. L.

2013-04-01

Alkali and alkaline earth metal impurities found in diesel fuels are potential poisons for diesel exhaust catalysts. A set of diesel engine production exhaust systems was aged to 150,000 miles. These exhaust systems included a diesel oxidation catalyst, selective catalytic reduction (SCR) catalyst, and diesel particulate filter (DPF). Four separate exhaust systems were aged, each with a different fuel: ultralow sulfur diesel containing no measureable metals, B20 (a common biodiesel blend) containing sodium, B20 containing potassium, and B20 containing calcium, which were selected to simulate the maximum allowable levels in B100 according to ASTM D6751. Analysis included Federal Test Proceduremore » emissions testing, bench-flow reactor testing of catalyst cores, electron probe microanalysis (EPMA), and measurement of thermo-mechanical properties of the DPFs. EPMA imaging found that the sodium and potassium penetrated into the washcoat, while calcium remained on the surface. Bench-flow reactor experiments were used to measure the standard nitrogen oxide (NOx) conversion, ammonia storage, and ammonia oxidation for each of the aged SCR catalysts. Vehicle emissions tests were conducted with each of the aged catalyst systems using a chassis dynamometer. The vehicle successfully passed the 0.2 gram/mile NOx emission standard with each of the four aged exhaust systems.« less

A new method to synthesize complicated multi-branched carbon nanotubes with controlled architecture and composition.

PubMed

Wei, Dacheng; Liu, Yunqi; Cao, Lingchao; Fu, Lei; Li, Xianglong; Wang, Yu; Yu, Gui; Zhu, Daoben

2006-02-01

Here we develop a simple method by using flow fluctuation to synthesize arrays of multi-branched carbon nanotubes (CNTs) that are far more complex than those previously reported. The architectures and compositions can be well controlled, thus avoiding any template or additive. A branching mechanism of fluctuation-promoted coalescence of catalyst particles is proposed. This finding will provide a hopeful approach to the goal of CNT-based integrated circuits and be valuable for applying branched junctions in nanoelectronics and producing branched junctions of other materials.

Insights on the SO2 Poisoning of Pt3Co/VC and Pt/VC Fuel Cell Catalysts

DTIC Science & Technology

2010-01-01

catalyst is performed at the cathode of proton exchange membrane fuel cells ( PEMFCs ) in order to link previously reported results at the elec- trode...stripping voltammetry and underpotential deposition (upd) of copper adatoms. Then the performance of PEMFC cathodes employing 30wt.% Pt3Co/VC and 50wt.% Pt/VC...proton exchange membrane fuel cells( PEMFCs )in order to link previously reported results at the elec- trode/solution interface to the FC environment. First

Exhaust emission control and diagnostics

DOEpatents

Mazur, Christopher John; Upadhyay, Devesh

2006-11-14

A diesel engine emission control system uses an upstream oxidation catalyst and a downstream SCR catalyst to reduce NOx in a lean exhaust gas environment. The engine and upstream oxidation catalyst are configured to provide approximately a 1:1 ratio of NO to NO2 entering the downstream catalyst. In this way, the downstream catalyst is insensitive to sulfur contamination, and also has improved overall catalyst NOx conversion efficiency. Degradation of the system is determined when the ratio provided is no longer near the desired 1:1 ratio. This condition is detected using measurements of engine operating conditions such as from a NOx sensor located downstream of the catalysts. Finally, control action to adjust an injected amount of reductant in the exhaust gas based on the actual NO to NO2 ratio upstream of the SCR catalyst and downstream of the oxidation catalyst.

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

Investigation of hybrid plasma-catalytic removal of acetone over CuO/γ-Al2O3 catalysts using response surface method.

PubMed

Zhu, Xinbo; Tu, Xin; Mei, Danhua; Zheng, Chenghang; Zhou, Jinsong; Gao, Xiang; Luo, Zhongyang; Ni, Mingjiang; Cen, Kefa

2016-07-01

In this work, plasma-catalytic removal of low concentrations of acetone over CuO/γ-Al2O3 catalysts was carried out in a cylindrical dielectric barrier discharge (DBD) reactor. The combination of plasma and the CuO/γ-Al2O3 catalysts significantly enhanced the removal efficiency of acetone compared to the plasma process using the pure γ-Al2O3 support, with the 5.0 wt% CuO/γ-Al2O3 catalyst exhibiting the best acetone removal efficiency of 67.9%. Catalyst characterization was carried out to understand the effect the catalyst properties had on the activity of the CuO/γ-Al2O3 catalysts in the plasma-catalytic reaction. The results indicated that the formation of surface oxygen species on the surface of the catalysts was crucial for the oxidation of acetone in the plasma-catalytic reaction. The effects that various operating parameters (discharge power, flow rate and initial concentration of acetone) and the interactions between these parameters had on the performance of the plasma-catalytic removal of acetone over the 5.0 wt% CuO/γ-Al2O3 catalyst were investigated using central composite design (CCD). The significance of the independent variables and their interactions were evaluated by means of the Analysis of Variance (ANOVA). The results showed that the gas flow rate was the most significant factor affecting the removal efficiency of acetone, whilst the initial concentration of acetone played the most important role in determining the energy efficiency of the plasma-catalytic process. Copyright © 2016 Elsevier Ltd. All rights reserved.

Methods and apparatus for carbon dioxide removal from a fluid stream

DOEpatents

Wei, Wei; Ruud, James Anthony; Ku, Anthony Yu-Chung; Ramaswamy, Vidya; Liu, Ke

2010-01-19

An apparatus for producing hydrogen gas wherein the apparatus includes a reactor. In one embodiment, the reactor includes at least two conversion-removal portions. Each conversion-removal portion comprises a catalyst section configured to convert CO in the stream to CO.sub.2 and a membrane section located downstream of and in flow communication with the catalyst section. The membrane section is configured to selectively remove the CO.sub.2 from the stream and to be in flow communication with a sweep gas.

Exploration of the Central Dogma at the Interface of Chemistry and Biology

PubMed Central

Zhou, Alice Qinhua

2010-01-01

Ever since the term “central dogma” was coined in 1958, researchers have sought to control information flow from nucleic acids to proteins. Talks delivered by Drs. Anna Pyle and Hiroaki Suga at this year’s Chemical Biology Symposium at Yale in May 2010 applauded recent advances in this area, at the interface between chemistry and biology. PMID:20885900

Electronic control of H+ current in a bioprotonic device with Gramicidin A and Alamethicin

NASA Astrophysics Data System (ADS)

Hemmatian, Zahra; Keene, Scott; Josberger, Erik; Miyake, Takeo; Arboleda, Carina; Soto-Rodríguez, Jessica; Baneyx, François; Rolandi, Marco

2016-10-01

In biological systems, intercellular communication is mediated by membrane proteins and ion channels that regulate traffic of ions and small molecules across cell membranes. A bioelectronic device with ion channels that control ionic flow across a supported lipid bilayer (SLB) should therefore be ideal for interfacing with biological systems. Here, we demonstrate a biotic-abiotic bioprotonic device with Pd contacts that regulates proton (H+) flow across an SLB incorporating the ion channels Gramicidin A (gA) and Alamethicin (ALM). We model the device characteristics using the Goldman-Hodgkin-Katz (GHK) solution to the Nernst-Planck equation for transport across the membrane. We derive the permeability for an SLB integrating gA and ALM and demonstrate pH control as a function of applied voltage and membrane permeability. This work opens the door to integrating more complex H+ channels at the Pd contact interface to produce responsive biotic-abiotic devices with increased functionality.

Synergetic effect at the interfaces of solution processed MoS2-WS2 composite for hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Kim, Seong Ku; Song, Wooseok; Ji, Seulgi; Lim, Yi Rang; Lee, Young Bum; Myung, Sung; Lim, Jongsun; An, Ki-Seok; Lee, Sun Sook

2017-12-01

Recently, the importance of developing an effective catalyst for hydrogen evolution reaction is emphasized because hydrogen fueled energy conversion processes are gaining attention as the next generation energy production method. We propose a transition metal dichalcogenide composite catalyst based on molybdenum disulfide (MoS2) and tungsten disulfide (WS2) on reduced graphene oxide coated nickel (rGO-Ni) foams. The composite exhibited enhanced catalytic activity with observed on-set potential of ∼275 mV at -10 mA/cm2 and Tafel slope of 54.1 mV/dec when the composition of the composite was 50%MoS2-50%WS2. The composite catalyst demonstrated high-stability up to 300 cycles. In order to understand the enhanced catalytic activity, X-ray photoelectron spectroscopy compositional analysis was utilized. We propose that the enhancement of catalytic activities exhibited by the composited samples were achieved due to introduction of new type of interface between MoS2 and WS2 grains, regional transition of 2H phase MoS2 and WS2 to 1T phase, and formation of excess sulfur which depended directly on the composition.

Geometric flow control of shear bands by suppression of viscous sliding

PubMed Central

Viswanathan, Koushik; Mahato, Anirban; Sundaram, Narayan K.; M'Saoubi, Rachid; Trumble, Kevin P.; Chandrasekar, Srinivasan

2016-01-01

Shear banding is a plastic flow instability with highly undesirable consequences for metals processing. While band characteristics have been well studied, general methods to control shear bands are presently lacking. Here, we use high-speed imaging and micro-marker analysis of flow in cutting to reveal the common fundamental mechanism underlying shear banding in metals. The flow unfolds in two distinct phases: an initiation phase followed by a viscous sliding phase in which most of the straining occurs. We show that the second sliding phase is well described by a simple model of two identical fluids being sheared across their interface. The equivalent shear band viscosity computed by fitting the model to experimental displacement profiles is very close in value to typical liquid metal viscosities. The observation of similar displacement profiles across different metals shows that specific microstructure details do not affect the second phase. This also suggests that the principal role of the initiation phase is to generate a weak interface that is susceptible to localized deformation. Importantly, by constraining the sliding phase, we demonstrate a material-agnostic method—passive geometric flow control—that effects complete band suppression in systems which otherwise fail via shear banding. PMID:27616920

A Catalyst-Free Amination of Functional Organolithium Reagents by Flow Chemistry.

PubMed

Kim, Heejin; Yonekura, Yuya; Yoshida, Jun-Ichi

2018-04-03

Reported is the electrophilic amination of functional organolithium intermediates with well-designed aminating reagents under mild reaction conditions using flow microreactors. The aminating reagents were optimized to achieve efficient C-N bond formation without using any catalyst. The electrophilic amination reactions of functionalized aryllithiums were successfully conducted under mild reaction conditions, within 1 minute, by using flow microreactors. The aminating reagent was also prepared by the flow method. Based on stopped-flow NMR analysis, the reaction time for the preparation of the aminating reagent was quickly optimized without the necessity of work-up. Integrated one-flow synthesis consisting of the generation of an aryllithium, the preparation of an aminating reagent, and their combined reaction was successfully achieved to give the desired amine within 5 minutes of total reaction time. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reactor for in situ measurements of spatially resolved kinetic data in heterogeneous catalysis

NASA Astrophysics Data System (ADS)

Horn, R.; Korup, O.; Geske, M.; Zavyalova, U.; Oprea, I.; Schlögl, R.

2010-06-01

The present work describes a reactor that allows in situ measurements of spatially resolved kinetic data in heterogeneous catalysis. The reactor design allows measurements up to temperatures of 1300 °C and 45 bar pressure, i.e., conditions of industrial relevance. The reactor involves reactants flowing through a solid catalyst bed containing a sampling capillary with a side sampling orifice through which a small fraction of the reacting fluid (gas or liquid) is transferred into an analytical device (e.g., mass spectrometer, gas chromatograph, high pressure liquid chromatograph) for quantitative analysis. The sampling capillary can be moved with μm resolution in or against flow direction to measure species profiles through the catalyst bed. Rotation of the sampling capillary allows averaging over several scan lines. The position of the sampling orifice is such that the capillary channel through the catalyst bed remains always occupied by the capillary preventing flow disturbance and fluid bypassing. The second function of the sampling capillary is to provide a well which can accommodate temperature probes such as a thermocouple or a pyrometer fiber. If a thermocouple is inserted in the sampling capillary and aligned with the sampling orifice fluid temperature profiles can be measured. A pyrometer fiber can be used to measure the temperature profile of the solid catalyst bed. Spatial profile measurements are demonstrated for methane oxidation on Pt and methane oxidative coupling on Li/MgO, both catalysts supported on reticulated α -Al2O3 foam supports.

Direct Synthetic Control over the Size, Composition, and Photocatalytic Activity of Octahedral Copper Oxide Materials: Correlation Between Surface Structure and Catalytic Functionality.

PubMed

Nguyen, Michelle A; Bedford, Nicholas M; Ren, Yang; Zahran, Elsayed M; Goodin, Robert C; Chagani, Fatima F; Bachas, Leonidas G; Knecht, Marc R

2015-06-24

We report a synthetic approach to form octahedral Cu2O microcrystals with a tunable edge length and demonstrate their use as catalysts for the photodegradation of aromatic organic compounds. In this particular study, the effects of the Cu(2+) and reductant concentrations and stoichiometric ratios were carefully examined to identify their roles in controlling the final material composition and size under sustainable reaction conditions. Varying the ratio and concentrations of Cu(2+) and reductant added during the synthesis determined the final morphology and composition of the structures. Octahedral particles were prepared at selected Cu(2+):glucose ratios that demonstrated a range of photocatalytic reactivity. The results indicate that material composition, surface area, and substrate charge effects play important roles in controlling the overall reaction rate. In addition, analysis of the post-reacted materials revealed photocorrosion was inhibited and that surface etching had preferentially occurred at the particle edges during the reaction, suggesting that the reaction predominately occurred at these interfaces. Such results advance the understanding of how size and composition affect the surface interface and catalytic functionality of materials.

A Virtual Instrument Panel and Serial Interface for the Parr 1672 Thermometer

ERIC Educational Resources Information Center

Salter, Gail; Range, Kevin; Salter, Carl

2005-01-01

The various features of a Visual Basic Program, which implements the 1672 Parr thermometer are described. The program permits remote control of the calorimetry experiment and also provides control for the flow of data and for file storage.

Direct growth and patterning of multilayer graphene onto a targeted substrate without an external carbon source.

PubMed

Kang, Dongseok; Kim, Won-Jun; Lim, Jung Ah; Song, Yong-Won

2012-07-25

Using only a simple tube furnace, we demonstrate the synthesis of patterned graphene directly on a designed substrate without the need for an external carbon source. Carbon atoms are absorbed onto Ni evaporator sources as impurities, and incorporated into catalyst layers during the deposition. Heat treatment conditions were optimized so that the atoms diffused out along the grain boundaries to form nanocrystals at the catalyst-substrate interfaces. Graphene patterns were obtained under patterned catalysts, which restricted graphene formation to within patterned areas. The resultant multilayer graphene was characterized by Raman spectroscopy and transmission electron microscopy to verify the high crystallinity and two-dimensional nanomorphology. Finally, a metal-semiconductor diode with a catalyst-graphene contact structure were fabricated and characterized to assess the semiconducting properties of the graphene sheets with respect to the display of asymmetric current-voltage behavior.

Effect of Gold Nanoparticles Addition to CuO–ZnO/A₂O₃ Catalyst in Conversion of Carbon Dioxide to Methanol.

PubMed

Kim, Ki-Joong; Ahn, Ho-Geun

2017-04-01

Hydrogenation of carbon dioxide (CO₂) into methanol (CH₃OH) was carried out in the CuO–ZnO based supported gold catalyst prepared by the co-precipitation method. When gold nanoparticles were added to the CuO–ZnO/Al2O₃ catalysts (CuO–ZnO/Au/Al₂O₃), the CO₂ conversion and CH₃OH yield were increased (two times higher than that of CuO–ZnO/Al₂O₃ catalyst) with increasing reaction pressure, but selectivity of CH3OH was decreased. The main reason of this result could suggest the importance gold-oxides interface in CH₃OH formation through hydrogenation of CO₂. Maximum selectivity and yield to CH₃OH over CuO–ZnO/Au/Al₂O₃ were obtained at 250°C and under 15–20 bars.

Response to Comment on "Active sites for CO2 hydrogenation to methanol on Cu/ZnO catalysts".

PubMed

Kattel, Shyam; Ramírez, Pedro J; Chen, Jingguang G; Rodriguez, José A; Liu, Ping

2017-09-01

In their Comment on the our recent Report, Nakamura et al argue that our x-ray photoelectron spectroscopy (XPS) analysis was affected by the presence of formate species on the catalyst surface. This argument is not valid because the reactant gases were evacuated at temperatures from 525 to 575 kelvin, conditions under which formate is not stable on the catalyst surface. An analysis of the XPS results obtained after exposing zinc oxide/copper (111) [ZnO/Cu(111)] surfaces to hydrogen (H 2 ) and mixtures of carbon dioxide (CO 2 )/H 2 show an absence of carbon (C) 1s signal, no asymmetries in the oxygen (O) 1s peak, and a Zn:O intensity close to 1:1. Thus, the most active phase of these catalysts contained a ZnO-Cu interface. Copyright © 2017, American Association for the Advancement of Science.

Flower-like Na2O nanotip synthesis via femtosecond laser ablation of glass

PubMed Central

2012-01-01

The current state-of-the-art in nanotip synthesis relies on techniques that utilize elaborate precursor chemicals, catalysts, or vacuum conditions, and any combination thereof. To realize their ultimate potential, synthesized nanotips require simpler fabrication techniques that allow for control over their final nano-morphology. We present a unique, dry, catalyst-free, and ambient condition method for creating densely clustered, flower-like, sodium oxide (Na2O) nanotips with controllable tip widths. Femtosecond laser ablation of a soda-lime glass substrate at a megahertz repetition rate, with nitrogen flow, was employed to generate nanotips with base and head widths as small as 100 and 20 nm respectively, and lengths as long as 10 μm. Control of the nanotip widths was demonstrated via laser dwell time with longer dwell times producing denser clusters of thinner nanotips. Energy dispersive X-ray analysis reveals that nanotip composition is Na2O. A new formation mechanism is proposed, involving an electrostatic effect between ionized nitrogen and polar Na2O. The synthesized nanotips may potentially be used in antibacterial and hydrogen storage applications. PMID:22809176

Engineering the Flow of Liquid Two-Phase Systems by Passive Noise Control

NASA Astrophysics Data System (ADS)

Zhang, Zeyi; Kong, Tiantian; Zhou, Chunmei; Wang, Liqiu

2018-02-01

We investigate a passive noise-control approach to engineering the two-phase flow in a microfluidic coflow system. The presence or absence of the jet breakup is studied for two immiscible oil phases, in a straight microchannel (referred to as the J device in the main text), an expansion microchannel (the W device) and a microchannel with the expansion-contraction geometry (the S device), respectively. We show that the jet breaks into droplets, in the jetting regime and the dripping regime (also referred to as the widening-jetting regime) for the straight channel and expansion channel, respectively, while a stable long jet does not break for the expansion-contraction geometry. As the inner phase passes the expansion-contraction functional unit, the random noise on the interface is significantly reduced and the hydrodynamic instability is suppressed, for a range of experimental parameters including flow rates, device geometry, liquid viscosity, and interfacial tension. We further present scale-up devices with multiple noise-control units and achieve decimeter-long yet stable jets. Our simple, effective, and robust noise-control approach can benefit microfluidic applications such as microfiber fabrication, interface chemical reaction, and on-chip distance transportation.

Synergistic effect of carbon nanofiber/nanotube composite catalyst on carbon felt electrode for high-performance all-vanadium redox flow battery.

PubMed

Park, Minjoon; Jung, Yang-jae; Kim, Jungyun; Lee, Ho il; Cho, Jeaphil

2013-10-09

Carbon nanofiber/nanotube (CNF/CNT) composite catalysts grown on carbon felt (CF), prepared from a simple way involving the thermal decomposition of acetylene gas over Ni catalysts, are studied as electrode materials in a vanadium redox flow battery. The electrode with the composite catalyst prepared at 700 °C (denoted as CNF/CNT-700) demonstrates the best electrocatalytic properties toward the V(2+)/V(3+) and VO(2+)/VO2(+) redox couples among the samples prepared at 500, 600, 700, and 800 °C. Moreover, this composite electrode in the full cell exhibits substantially improved discharge capacity and energy efficiency by ~64% and by ~25% at 40 mA·cm(-2) and 100 mA·cm(-2), respectively, compared to untreated CF electrode. This outstanding performance is due to the enhanced surface defect sites of exposed edge plane in CNF and a fast electron transfer rate of in-plane side wall of the CNT.

Software defined network architecture based research on load balancing strategy

NASA Astrophysics Data System (ADS)

You, Xiaoqian; Wu, Yang

2018-05-01

As a new type network architecture, software defined network has the key idea of separating the control place of the network from the transmission plane, to manage and control the network in a concentrated way; in addition, the network interface is opened on the control layer and the data layer, so as to achieve programmable control of the network. Considering that only the single shortest route is taken into the calculation of traditional network data flow transmission, and congestion and resource consumption caused by excessive load of link circuits are ignored, a link circuit load based flow media business QoS gurantee system is proposed in this article to divide the flow in the network into ordinary data flow and QoS flow. In this way, it supervises the link circuit load with the controller so as to calculate reasonable route rapidly and issue the flow table to the exchanger, to finish rapid data transmission. In addition, it establishes a simulation platform to acquire optimized result through simulation experiment.

First-principles quantum mechanical investigations: Catalytic reactions of furfural on Pd(111) and at the water/Pd(111) interface

NASA Astrophysics Data System (ADS)

Xue, Wenhua

Bio-oils have drawn more and more attention from scientists as a promising new clean, cheap energy source. One of the most interesting relevant issues is the effect of catalysts on the catalytic reactions that are used for producing bio-oils. Furfural, as a very important intermediate during these reactions, has attracted significant studies. However, the effect of catalysts, including particularly the liquid/solid interface formed by a metal catalyst and liquid water, in the catalytic reactions involving furfural still remains elusive. In this research, we performed ab initio molecular dynamics simulations and first-principles density-functional theory calculations to investigate the atomic-scale mechanisms of catalytic hydrogenation of furfural on the palladium surface and at the liquid/state interface formed by the palladium surface and liquid water. We studied all the possible mechanisms that lead to formation of furfuryl alcohol (FOL), formation of tetrahydrofurfural (THFAL), and formation of tetrahydrofurfurfuryl alcohol (THFOL). We found that liquid water plays a significant role in the hydrogenation reactions. During the reaction in the presence of water and the palladium catalyst, in particular, water directly participates in the hydrogenation of the aldehyde group of furfural and facilitates the formation of FOL by reducing the activation energy. Our calculations show that water provides hydrogen for the hydrogenation of the aldehyde group, and at the same time, a pre-existing hydrogen atom, which is resulted from dissociation of molecular hydrogen (experimentally, molecular hydrogen is always supplied for hydrogenation) on the palladium surface, is bonded to water, making the water molecule intact in structure. In the absence of water, on the other hand, formation of FOL and THFAL on the palladium surface involves almost the same energy barriers, suggesting a comparable selectivity. Overall, as water reduces the activation energy for the formation of FOL while increases the energy barrier slightly for hydrogenation of the furan ring, water changes the reaction selectivity and promotes the formation of furfuryl alcohol.

Effects of Mobile Phone-Based App Learning Compared to Computer-Based Web Learning on Nursing Students: Pilot Randomized Controlled Trial

PubMed Central

2015-01-01

Objectives This study aimed to determine the effect of mobile-based discussion versus computer-based discussion on self-directed learning readiness, academic motivation, learner-interface interaction, and flow state. Methods This randomized controlled trial was conducted at one university. Eighty-six nursing students who were able to use a computer, had home Internet access, and used a mobile phone were recruited. Participants were randomly assigned to either the mobile phone app-based discussion group (n = 45) or a computer web-based discussion group (n = 41). The effect was measured at before and after an online discussion via self-reported surveys that addressed academic motivation, self-directed learning readiness, time distortion, learner-learner interaction, learner-interface interaction, and flow state. Results The change in extrinsic motivation on identified regulation in the academic motivation (p = 0.011) as well as independence and ability to use basic study (p = 0.047) and positive orientation to the future in self-directed learning readiness (p = 0.021) from pre-intervention to post-intervention was significantly more positive in the mobile phone app-based group compared to the computer web-based discussion group. Interaction between learner and interface (p = 0.002), having clear goals (p = 0.012), and giving and receiving unambiguous feedback (p = 0.049) in flow state was significantly higher in the mobile phone app-based discussion group than it was in the computer web-based discussion group at post-test. Conclusions The mobile phone might offer more valuable learning opportunities for discussion teaching and learning methods in terms of self-directed learning readiness, academic motivation, learner-interface interaction, and the flow state of the learning process compared to the computer. PMID:25995965

Artificial plasma cusp generated by upper hybrid instabilities in HF heating experiments at HAARP

NASA Astrophysics Data System (ADS)

Kuo, Spencer; Snyder, Arnold

2013-05-01

High Frequency Active Auroral Research Program digisonde was operated in a fast mode to record ionospheric modifications by the HF heating wave. With the O mode heater of 3.2 MHz turned on for 2 min, significant virtual height spread was observed in the heater off ionograms, acquired beginning the moment the heater turned off. Moreover, there is a noticeable bump in the virtual height spread of the ionogram trace that appears next to the plasma frequency (~ 2.88 MHz) of the upper hybrid resonance layer of the HF heating wave. The enhanced spread and the bump disappear in the subsequent heater off ionograms recorded 1 min later. The height distribution of the ionosphere in the spread situation indicates that both electron density and temperature increases exceed 10% over a large altitude region (> 30 km) from below to above the upper hybrid resonance layer. This "mini cusp" (bump) is similar to the cusp occurring in daytime ionograms at the F1-F2 layer transition, indicating that there is a small ledge in the density profile reminiscent of F1-F2 layer transitions. Two parametric processes exciting upper hybrid waves as the sidebands by the HF heating waves are studied. Field-aligned purely growing mode and lower hybrid wave are the respective decay modes. The excited upper hybrid and lower hybrid waves introduce the anomalous electron heating which results in the ionization enhancement and localized density ledge. The large-scale density irregularities formed in the heat flow, together with the density irregularities formed through the parametric instability, give rise to the enhanced virtual height spread. The results of upper hybrid instability analysis are also applied to explain the descending feature in the development of the artificial ionization layers observed in electron cyclotron harmonic resonance heating experiments.

Energetic Neutral Atom Spectra in the 0.2-3.0 keV from a Residual Source Across the Sky Obtained by the Neutral Particle Detector on board Venus Express

NASA Astrophysics Data System (ADS)

Brandt, Pontus; Roelof, Edmond; Wurz, Peter; Decker, Robert; Barabash, Stas; Bazell, David; Sotirelis, Thomas

We have surveyed the sky for residual energetic neutral atom (ENA) signals in the energy range of 0.2-3.0 keV [Brandt et al., AIP Proceedings, 2009]. Approximately three years of data obtained by the Neutral Particle Detector (NPD) on board Venus Express (VEX) from May 2006 through August 2009 have been analyzed. After applying strict viewing criteria to minimize all known signals and subtracting the UV background from the Milky Way, we find a residual energy spectral shape with a ledge/bump at around 0.5 keV and a break in the spectral slope at about 1.0 keV, reiminiscent of the spectral shape obtained in reverse shocks. The ledge/bump at about 0.5 keV appears consistent with twice the plasma flow velocity obtained by the V1 measurements in the inner HS. When the ENA spectrum is divided by the energy dependent charge exchange cross section its slope above 1 keV has a spectral power-law index of 1.5, with some variations across the sky. In order to better understand the spectral shape over an extended energy range we compare the spectra obtained by VEX/NPD with the ones reported by the Interstellar Boundary Explorer (IBEX) [Funsten et al., Science, 2009], by the Ion Neutral Camera (INCA) on board Cassini [Krimigis et al., Science, 2009]and with those measured in-situ in the inner heliosheath (HS) by the Low-Energy Charged Particle (LECP) instrument (>40 keV) on board Voyager-1 (V1).

Fabrication and Characterization of New Composite Tio2 Carbon Nanofiber Anodic Catalyst Support for Direct Methanol Fuel Cell via Electrospinning Method.

PubMed

Abdullah, N; Kamarudin, S K; Shyuan, L K; Karim, N A

2017-12-06

Platinum (Pt) is the common catalyst used in a direct methanol fuel cell (DMFC). However, Pt can lead towards catalyst poisoning by carbonaceous species, thus reduces the performance of DMFC. Thus, this study focuses on the fabrication of a new composite TiO 2 carbon nanofiber anodic catalyst support for direct methanol fuel cells (DMFCs) via electrospinning technique. The distance between the tip and the collector (DTC) and the flow rate were examined as influencing parameters in the electrospinning technique. To ensure that the best catalytic material is fabricated, the nanofiber underwent several characterizations and electrochemical tests, including FTIR, XRD, FESEM, TEM, and cyclic voltammetry. The results show that D18, fabricated with a flow rate of 0.1 mLhr -1 and DTC of 18 cm, is an ultrafine nanofiber with the smallest average diameter, 136.73 ± 39.56 nm. It presented the highest catalyst activity and electrochemical active surface area value as 274.72 mAmg -1 and 226.75m 2  g -1 PtRu , respectively, compared with the other samples.

Catalytic wet oxidation of phenol in a trickle bed reactor over a Pt/TiO2 catalyst.

PubMed

Maugans, Clayton B; Akgerman, Aydin

2003-01-01

Catalytic wet oxidation of phenol was studied in a batch and a trickle bed reactor using 4.45% Pt/TiO2 catalyst in the temperature range 150-205 degrees C. Kinetic data were obtained from batch reactor studies and used to model the reaction kinetics for phenol disappearance and for total organic carbon disappearance. Trickle bed experiments were then performed to generate data from a heterogeneous flow reactor. Catalyst deactivation was observed in the trickle bed reactor, although the exact cause was not determined. Deactivation was observed to linearly increase with the cumulative amount of phenol that had passed over the catalyst bed. Trickle bed reactor modeling was performed using a three-phase heterogeneous model. Model parameters were determined from literature correlations, batch derived kinetic data, and trickle bed derived catalyst deactivation data. The model equations were solved using orthogonal collocations on finite elements. Trickle bed performance was successfully predicted using the batch derived kinetic model and the three-phase reactor model. Thus, using the kinetics determined from limited data in the batch mode, it is possible to predict continuous flow multiphase reactor performance.

Surface science approach to Pt/carbon model catalysts: XPS, STM and microreactor studies

NASA Astrophysics Data System (ADS)

Motin, Abdul Md.; Haunold, Thomas; Bukhtiyarov, Andrey V.; Bera, Abhijit; Rameshan, Christoph; Rupprechter, Günther

2018-05-01

Pt nanoparticles supported on carbon are an important technological catalyst. A corresponding model catalyst was prepared by physical vapor deposition (PVD) of Pt on sputtered HOPG (highly oriented pyrolytic graphite). The carbon substrate before and after sputtering as well as the Pt/HOPG system before and after Pt deposition and annealing were examined by XPS and STM. This yielded information on the surface density of defects, which serve as nucleation centres for Pt, and on the size distribution (mean size/height) of the Pt nanoparticles. Two different model catalysts were prepared with mean sizes of 2.0 and 3.6 nm, both turned out to be stable upon UHV-annealing to 300 °C. After transfer into a UHV-compatible flow microreactor and subsequent cleaning in UHV and under mbar pressure, the catalytic activity of the Pt/HOPG model system for ethylene hydrogenation was examined under atmospheric pressure flow conditions. This enabled to determine temperature-dependent conversion rates, turnover frequencies (TOFs) and activation energies. The catalytic results obtained are in line with the characteristics of technological Pt/C, demonstrating the validity of the current surface science based model catalyst approach.

Comparison of non-catalytic and catalytic fast pyrolysis of corncob in a fluidized bed reactor.

PubMed

Zhang, Huiyan; Xiao, Rui; Huang, He; Xiao, Gang

2009-02-01

Fast pyrolysis of corncob with and without catalyst was investigated in a fluidized bed to determine the effects of pyrolysis parameters (temperature, gas flow rate, static bed height and particle size) and a HZSM-5 zeolite catalyst on the product yields and the qualities of the liquid products. The result showed that the optimal conditions for liquid yield (56.8%) were a pyrolysis temperature of 550 degrees C, gas flow rate of 3.4 L/min, static bed height of 10 cm and particle size of 1.0-2.0mm. The presence of the catalyst increased the yields of non-condensable gas, water and coke, while decreased the liquid and char yields. The elemental analysis showed that more than 25% decrease in oxygen content of the collected liquid in the second condenser with HZSM-5 was observed compared with that without catalyst. The H/C, O/C molar ratios and the higher heating value of the oil fraction in the collected liquid with the catalyst were 1.511, 0.149 and 34.6 MJ/kg, respectively. It was indicated that the collected liquid in the second condenser had high qualities and might be used as transport oil.

Space and time-resolved probing of heterogeneous catalysis reactions using lab-on-a-chip

NASA Astrophysics Data System (ADS)

Navin, Chelliah V.; Krishna, Katla Sai; Theegala, Chandra S.; Kumar, Challa S. S. R.

2016-03-01

Probing catalytic reactions on a catalyst surface in real time is a major challenge. Herein, we demonstrate the utility of a continuous flow millifluidic chip reactor coated with a nanostructured gold catalyst as an effective platform for in situ investigation of the kinetics of catalytic reactions by taking 5-(hydroxymethyl)furfural (HMF) to 2,5-furandicarboxylic acid (FDCA) conversion as a model reaction. The idea conceptualized in this paper can not only dramatically change the ability to probe the time-resolved kinetics of heterogeneous catalysis reactions but also used for investigating other chemical and biological catalytic processes, thereby making this a broad platform for probing reactions as they occur within continuous flow reactors.Probing catalytic reactions on a catalyst surface in real time is a major challenge. Herein, we demonstrate the utility of a continuous flow millifluidic chip reactor coated with a nanostructured gold catalyst as an effective platform for in situ investigation of the kinetics of catalytic reactions by taking 5-(hydroxymethyl)furfural (HMF) to 2,5-furandicarboxylic acid (FDCA) conversion as a model reaction. The idea conceptualized in this paper can not only dramatically change the ability to probe the time-resolved kinetics of heterogeneous catalysis reactions but also used for investigating other chemical and biological catalytic processes, thereby making this a broad platform for probing reactions as they occur within continuous flow reactors. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06752a

Reduction of CO2 to low carbon alcohols on CuO FCs/Fe2O3 NTs catalyst with photoelectric dual catalytic interfaces

NASA Astrophysics Data System (ADS)

Li, Peiqiang; Wang, Huying; Xu, Jinfeng; Jing, Hua; Zhang, Jun; Han, Haixiang; Lu, Fusui

2013-11-01

In this paper, the CuO FCs/Fe2O3 NTs catalyst was obtained after Fe2O3 nanotubes (Fe2O3 NTs) were decorated with CuO flower clusters (CuO FCs) by the pulse electrochemical deposition method. The in situ vertically aligned Fe2O3 NTs were prepared on the ferrous substrate by a potentiostatic anodization method. The SEM result showed the volcano-like Fe2O3 NTs were arranged in order and the CuO FCs constituted of flaky CuO distributed on the Fe2O3 NTs surface uniformly. After CuO FCs were loaded on Fe2O3 NTs, the absorption of visible light was enhanced noticeably, and its band gap narrowed to 1.78 eV from 2.03 eV. The conduction band and valence band locating at -0.73 eV and 1.05 eV, respectively were further obtained. In the PEC reduction of CO2 process, methanol and ethanol were two major products identified by chromatography. Their contents reached 1.00 mmol L-1 cm-2 and 107.38 μmol L-1 cm-2 after 6 h, respectively. This high-efficiency catalyst with photoelectric dual catalytic interfaces has a great guidance and reference significance for CO2 reduction to liquid carbon fuels.In this paper, the CuO FCs/Fe2O3 NTs catalyst was obtained after Fe2O3 nanotubes (Fe2O3 NTs) were decorated with CuO flower clusters (CuO FCs) by the pulse electrochemical deposition method. The in situ vertically aligned Fe2O3 NTs were prepared on the ferrous substrate by a potentiostatic anodization method. The SEM result showed the volcano-like Fe2O3 NTs were arranged in order and the CuO FCs constituted of flaky CuO distributed on the Fe2O3 NTs surface uniformly. After CuO FCs were loaded on Fe2O3 NTs, the absorption of visible light was enhanced noticeably, and its band gap narrowed to 1.78 eV from 2.03 eV. The conduction band and valence band locating at -0.73 eV and 1.05 eV, respectively were further obtained. In the PEC reduction of CO2 process, methanol and ethanol were two major products identified by chromatography. Their contents reached 1.00 mmol L-1 cm-2 and 107.38 μmol L-1 cm-2 after 6 h, respectively. This high-efficiency catalyst with photoelectric dual catalytic interfaces has a great guidance and reference significance for CO2 reduction to liquid carbon fuels. Electronic supplementary information (ESI) available: Reduction of CO2 to low carbon alcohols on CuO FCs/Fe2O3 NTs catalyst with photoelectric dual catalytic interfaces. See DOI: 10.1039/c3nr03352j

Synthesis and characterization of nanoscale molybdenum sulfide catalysts by controlled gas phase decomposition of Mo(CO){sub 6} and H{sub 2}S

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

Close, M.R.; Petersen, J.L.; Kugler, E.L.

1999-04-05

Molybdenum sulfide catalysts with surface areas ranging from 16 to 120 m{sup 2}/g were prepared by the thermal decomposition of Mo(CO){sub 6} and H{sub 2}S vapors in a specially designed tubular reactor system. The gas phase decomposition (GPD) reactions performed at 500--1100 C produced only MoS{sub 2} when excess H{sub 2}S was used. The optimum temperature range for the high-yield production of MoS{sub 2} was from 500 to 700 C. By controlling the decomposition temperature, the Mo(CO){sub 6} partial pressure, or the inert gas flow rate, the surface area, oxidation state, chemical composition, and the grain size of the molybdenummore » sulfide product(s) were modified. At reactor temperatures between 300 and 400 C, lower valent molybdenum sulfide materials, which were sulfur deficient relative to MoS{sub 2}, were obtained with formal molybdenum oxidation states intermediate to those found for Chevrel phase compounds, M{prime}Mo{sub 6}S{sub 8} (M{prime} = Fe, Ni, Co) and MoS{sub 2}. By lowering the H{sub 2}S flow rate used for the GPD reaction at 1000 C, mixtures containing variable amounts of MoS{sub 2} and Mo{sub 2}S{sub 3} were produced. Thus, through the modification of critical reactor parameters used for these GPD reactions, fundamental material properties were controlled.« less

A Full Body Steerable Wind Display for a Locomotion Interface.

PubMed

Kulkarni, Sandip D; Fisher, Charles J; Lefler, Price; Desai, Aditya; Chakravarthy, Shanthanu; Pardyjak, Eric R; Minor, Mark A; Hollerbach, John M

2015-10-01

This paper presents the Treadport Active Wind Tunnel (TPAWT)-a full-body immersive virtual environment for the Treadport locomotion interface designed for generating wind on a user from any frontal direction at speeds up to 20 kph. The goal is to simulate the experience of realistic wind while walking in an outdoor virtual environment. A recirculating-type wind tunnel was created around the pre-existing Treadport installation by adding a large fan, ducting, and enclosure walls. Two sheets of air in a non-intrusive design flow along the side screens of the back-projection CAVE-like visual display, where they impinge and mix at the front screen to redirect towards the user in a full-body cross-section. By varying the flow conditions of the air sheets, the direction and speed of wind at the user are controlled. Design challenges to fit the wind tunnel in the pre-existing facility, and to manage turbulence to achieve stable and steerable flow, were overcome. The controller performance for wind speed and direction is demonstrated experimentally.

Macrokinetics of carbon nanotubes synthesis by the chemical vapor deposition method

NASA Astrophysics Data System (ADS)

Rukhov, Artem; Dyachkova, Tatyana; Tugolukov, Evgeny; Besperstova, Galina

2017-11-01

A new approach to studying and developing basic processes which take place on the surface of a metal catalyst during the thermal decomposition of carbonaceous substances in the carbon nanotubes synthesis by the chemical vapor deposition method was proposed. In addition, an analysis was made of the interrelationships between these thermal, diffusion, hydrodynamic and other synthesis processes. A strong effect of the catalyst regeneration stage on the stage of nanotube formation has been shown. Based on the developed approach, a mathematical model was elaborated. Comparison of the calculation and the experiment carried out with the NiO-MgO catalyst at propane flow rate of 50 mL/min (standard conditions) and ethanol flow rate 0.3 mL/min (liq.) has revealed a discrepancy of less than 10%.

One step bioconversion of waste precious metals into Serratia biofilm-immobilized catalyst for Cr(VI) reduction.

PubMed

Yong, P; Liu, W; Zhang, Z; Beauregard, D; Johns, M L; Macaskie, L E

2015-11-01

For reduction of Cr(VI) the Pd-catalyst is excellent but costly. The objectives were to prove the robustness of a Serratia biofilm as a support for biogenic Pd-nanoparticles and to fabricate effective catalyst from precious metal waste. Nanoparticles (NPs) of palladium were immobilized on polyurethane reticulated foam and polypropylene supports via adhesive biofilm of a Serratia sp. The biofilm adhesion and cohesion strength were unaffected by palladization and catalytic biofilm integrity was also shown by magnetic resonance imaging. Biofilm-Pd and mixed precious metals on biofilm (biofilm-PM) reduced 5 mM Cr(VI) to Cr(III) when immobilized in a flow-through column reactor, at respective flow rates of 9 and 6 ml/h. The lower activity of the latter was attributed to fewer, larger, metal deposits on the bacteria. Activity was lost in each case at pH 7 but was restored by washing with 5 mM citrate solution or by exposure of columns to solution at pH 2, suggesting fouling by Cr(III) hydroxide product at neutral pH. A 'one pot' conversion of precious metal waste into new catalyst for waste decontamination was shown in a continuous flow system based on the use of Serratia biofilm to manufacture and support catalytic Pd-nanoparticles.

A hard-soft microfluidic-based biosensor flow cell for SPR imaging application.

PubMed

Liu, Changchun; Cui, Dafu; Li, Hui

2010-09-15

An ideal microfluidic-based biosensor flow cell should have not only a "soft" interface for high strength sealing with biosensing chips, but also "hard" macro-to-micro interface for tubing connection. Since these properties are exclusive of each other, no one material can provide the advantages of both. In this paper, we explore the application of a SiO(2) thin film, deposited by plasma-enhanced chemical vapor deposition (PECVD) technology, as an intermediate layer for irreversibly adhering polydimethylsiloxane (PDMS) to plastic substrate, and develop a hard-soft, compact, robust microfluidic-based biosensor flow cell for the multi-array immunoassay application of surface plasmon resonance (SPR) imaging. This hard-soft biosensor flow cell consists of one rigid, computer numerically controlled (CNC)-machined poly(methyl methacrylate) (PMMA) base coated with a 200 nm thick SiO(2) thin film, and one soft PDMS microfluidic layer. This novel microfluidic-based biosensor flow cell does not only keep the original advantage of conventional PDMS-based biosensor flow cell such as the intrinsically soft interface, easy-to-fabrication, and low cost, but also has a rigid, robust, easy-to-use interface to tubing connection and can be operated up to 185 kPa in aqueous environments without failure. Its application was successfully demonstrated with two types of experiments by coupling with SPR imaging biosensor: the real-time monitoring of the immunoglobulin G (IgG) interaction, as well as the detection of sulfamethoxazole (SMOZ) and sulfamethazine (SMZ) with the sensitivity of 3.5 and 0.6 ng/mL, respectively. This novel hard-soft microfluidic device is also useful for a variety of other biosensor flow cells. Copyright 2010 Elsevier B.V. All rights reserved.

Investigating the performance of catalyst layer micro-structures with different platinum loadings

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

Khakaz-Baboli, Moben; Harvey, David; Pharoah, Jon

In this study a four-phase micro-structure of a PEFC catalyst layer was reconstructed by randomly placing overlapping spheres for each solid catalyst phase. The micro-structure was mirrored to make a micro-structure. A body-fit computational mesh was produced for the reconstructed micro-structure in OpenFOAM. Associated conservation equations were solved within all the phases with electrochemical reaction as the boundary condition at the interface between ionomer and platinum phases. The study is focused on the platinum loading of CL. The polarization curves of the micro-structure performance have been compared for different platinum loadings. This paper gives increased insight into the relatively greatermore » losses at decreased platinum loadings.« less

Effect of Interface Shape and Magnetic Field on the Microstructure of Bulk Ge:Ga

NASA Technical Reports Server (NTRS)

Cobb, S. D.; Szofran, F. R.; Volz, M. P.

1999-01-01

Thermal and compositional gradients induced during the growth process contribute significantly to the development of defects in the solidified boule. Thermal gradients and the solid-liquid interface shape can be greatly effected by ampoule material. Compositional gradients are strongly influenced by interface curvature and convective flow in the liquid. Results of this investigation illustrate the combined influences of interface shape and convective fluid flow. An applied magnetic field was used to reduce the effects of convective fluid flow in the electrically conductive melt during directional solidification. Several 8 mm diameter boules of Ga-doped Ge were grown at different field strengths, up to 5 Tesla, in four different ampoule materials. Compositional profiles indicate mass transfer conditions ranged from completely mixed to diffusion controlled. The influence of convection in the melt on the developing crystal microstructure and defect density was investigated as a function of field strength and ampoule material. Chemical etching and electron backscattered electron diffraction were used to map the crystal structure of each boule along the center plane. Dislocation etch pit densities were measured for each boule. Results show the influence of magnetic field strength and ampoule material on overall crystal quality.

Numerical simulations of the process of multiple shock-flame interactions

NASA Astrophysics Data System (ADS)

Jiang, Hua; Dong, Gang; chen, Xiao; Wu, Jin-Tao

2016-08-01

Based on a weighted essentially nonoscillatory scheme, the multiple interactions of a flame interface with an incident shock wave and its reshock waves are numerically simulated by solving the compressible reactive Navier-Stokes equations with a single-step Arrhenius chemical reaction. The two-dimensional sinusoidally perturbed premixed flames with different initial perturbed amplitudes are used to investigate the effect of the initial perturbation on the flame evolutions. The results show that the development of the flame interface is directly affected by the initial perturbed amplitudes before the passages of reshock waves, and the perturbation development is mainly controlled by the Richtmyer-Meshkov instability (RMI). After the successive impacts of multiple reshock waves, the chemical reaction accelerates the consumption of reactants and leads to a gradual disappearance of the initial perturbed information. The perturbation developments in frozen flows with the same initial interface as those in reactive flows are also demonstrated. Comparisons of results between the reactive and frozen flows show that a chemical reaction changes the perturbation pattern of the flame interface by decreasing the density gradient, thereby weakening the baroclinic torque in the flame mixing region, and therefore plays a dominant role after the passage of reshock waves.

Microkinetic modeling of H 2SO 4 formation on Pt based diesel oxidation catalysts

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

Sharma, Hom N.; Sun, Yunwei; Glascoe, Elizabeth A.

The presence of water vapor and sulfur oxides in diesel engine exhaust leads to the formation of sulfuric acid (H 2SO 4), which severely impacts the performance of Pt/Pd based emissions aftertreatment catalysts. In this study, a microkinetic model is developed to investigate the reaction pathways of H 2SO 4 formation on Pt based diesel oxidation catalysts (DOCs). The microkinetic model consists of 14 elementary step reactions (7 reversible pairs) and yields prediction in excellent agreement with data obtained from experiments at practically relevant sulfur oxides environment in engine exhaust. The model simulation utilizing a steady-state plug flow reactor demonstratesmore » that it matches experimental data in both kinetically and thermodynamically controlled regions. Results clearly show the negative impact of SO 3 on the SO 2 oxidation light-off temperature, consistent with experimental observations. A reaction pathway analysis shows that the primary pathway of sulfuric acid formation on Pt surface involves SO 2* oxidation to form SO 3* with the subsequent interaction of SO 3* with H 2O* to form H 2SO 4*.« less

Microkinetic modeling of H 2SO 4 formation on Pt based diesel oxidation catalysts

DOE PAGES

Sharma, Hom N.; Sun, Yunwei; Glascoe, Elizabeth A.

2017-08-10

The presence of water vapor and sulfur oxides in diesel engine exhaust leads to the formation of sulfuric acid (H 2SO 4), which severely impacts the performance of Pt/Pd based emissions aftertreatment catalysts. In this study, a microkinetic model is developed to investigate the reaction pathways of H 2SO 4 formation on Pt based diesel oxidation catalysts (DOCs). The microkinetic model consists of 14 elementary step reactions (7 reversible pairs) and yields prediction in excellent agreement with data obtained from experiments at practically relevant sulfur oxides environment in engine exhaust. The model simulation utilizing a steady-state plug flow reactor demonstratesmore » that it matches experimental data in both kinetically and thermodynamically controlled regions. Results clearly show the negative impact of SO 3 on the SO 2 oxidation light-off temperature, consistent with experimental observations. A reaction pathway analysis shows that the primary pathway of sulfuric acid formation on Pt surface involves SO 2* oxidation to form SO 3* with the subsequent interaction of SO 3* with H 2O* to form H 2SO 4*.« less

Enhanced TiO2 Photocatalytic Processing of Organic Wastes for Green Space Exploration

NASA Technical Reports Server (NTRS)

Udom, I.; Goswami, D. Y.; Ram, M. K.; Stefanakos, E. K.; Heep, A. F.; Kulis, M. J.; McNatt, J. S.; Jaworske, D. A.; Jones, C. A.

2013-01-01

The effect of transition metal co-catalysts on the photocatalytic properties of TiO2 was investigated. Ruthenium (Ru), palladium, platinum, copper, silver, and gold, were loaded onto TiO2 powders (anatase and mixed-phase P25) and screened for the decomposition of rhodamine B (RhB) under broad-band irradiation. The morphology and estimated chemical composition of photocatalysts were determined by scanning electron microscopy and energy dispersive spectroscopy, respectively. Brunhauer, Emmett and Teller (BET) analysis measured mass-specific surface area(s). X-ray diffraction analysis was performed to confirm the identity of titania phase(s) present. The BET surface area of anatase TiO2/Ru 1% (9.2 sq m/gm) was one of the highest measured of all photocatalysts prepared in our laboratory. Photolyses conducted under air-saturated and nitrogen-saturated conditions revealed photodegradation efficiencies of 85 and 2 percent, respectively, after 60 min compared to 58 percent with no catalyst. The cause of low photocatalytic activity under an inert atmosphere is discussed. TiO2/Ru 1% showed a superior photocatalytic activity relative to P25-TiO2 under broad-band irradiation. A potential deployment of photocatalytic technologies on a mission could be a reactor with modest enhancement in solar intensity brought about by a trough-style reactor, with reactants and catalyst flowing along the axis of the trough and therefore being illuminated for a controlled duration based on the flow rate.

DEVELOPMENT OF TRANSITION METAL OXIDE-ZEOLITE CATALYSTS TO CONTROL CHLORINATED VOC AIR EMISSIONS

EPA Science Inventory

The paper discusses the development of transition metal oxide (TMO)-zeolite oxidation catalysts to control chlorinated volatile organic compound (CVOC) air emissions. esearch has been initiated to enhance the utility of these catalysts by the development of a sorption-catalyst sy...

Simulating Lahars Using A Rotating Drum

NASA Astrophysics Data System (ADS)

Neather, Adam; Lube, Gert; Jones, Jim; Cronin, Shane

2014-05-01

A large (0.5 m in diameter, 0.15 m wide) rotating drum is used to investigate the erosion and deposition mechanics of lahars. To systematically simulate the conditions occurring in natural mass flows our experimental setup differs from the common rotating drum employed in industrial/engineering studies. Natural materials with their typical friction properties are used, as opposed to the frequently employed spherical glass beads; the drum is completely water-proof, so solid/air and solid/liquid mixtures can be investigated; the drum velocity and acceleration can be precisely controlled using a software interface to a micro-controller, allowing for the study of steady, unsteady and intermediate flow regimes. The drum has a toughened glass door, allowing high-resolution, high-speed video recording of the material inside. Vector maps of the velocities involved in the flows are obtained using particle image velocimetry (PIV). The changes in velocity direction and/or magnitude are used to locate the primary internal boundaries between layers of opposite flow direction, as well as secondary interfaces between shear layers. A range of variables can be measured: thickness and number of layers; the curvature of the free surface; frequency of avalanching; position of the centre of mass of the material; and the velocity profiles of the flowing material. Experiments to date have focussed on dry materials, and have had a fill factor of approximately 0.3. Combining these measured variables allows us to derive additional data of interest, such as mass and momentum flux. It is these fluxes that we propose will allow insight into the erosion/deposition mechanics of a lahar. A number of conclusions can be drawn to date. A primary interface separates flowing and passive region (this interface has been identified in previous studies). As well as the primary interface, the flowing layer separates into individual shear layers, with individual erosion/deposition and flow histories. This complex flow geometry and process of erosion and deposition seen in our high speed videos is more complicated than previously reported in the literature. We identify two layers only in the slowest flows (< 0.5 rad s-1), while faster ones (< 4 rad s-1) include between three and five. As the rotational velocity of the drum increases, the curvature of the free surface increases. In the central part of the drum, the primary interfaces occasionally merges into an elliptical zone rather than a linear shear boundary. Inside this zone is a complete circulation of material. These zones' size and number appears to be a function of the rotational velocity of the drum. These "Neather cells" (as we tentatively name these phenomena) can reach as large as 20 mm in thickness. The centre of mass' deflection from vertical is linearly dependent on rotational velocity, whilst the typical flow regimes as identified by Mellmann [2001] show no influence. The frequency of avalanches increases with velocity up to a critical velocity (approximately 1.1 rad s-1), after which the avalanche frequency remains constant. 1 References J Mellmann. The transverse motion of solids in rotating cylinders-forms of motion and transition behavior. Powder Technology, 118(3):251-270, 2001.

Measurement and control systems for an imaging electromagnetic flow metre.

PubMed

Zhao, Y Y; Lucas, G; Leeungculsatien, T

2014-03-01

Electromagnetic flow metres based on the principles of Faraday's laws of induction have been used successfully in many industries. The conventional electromagnetic flow metre can measure the mean liquid velocity in axisymmetric single phase flows. However, in order to achieve velocity profile measurements in single phase flows with non-uniform velocity profiles, a novel imaging electromagnetic flow metre (IEF) has been developed which is described in this paper. The novel electromagnetic flow metre which is based on the 'weight value' theory to reconstruct velocity profiles is interfaced with a 'Microrobotics VM1' microcontroller as a stand-alone unit. The work undertaken in the paper demonstrates that an imaging electromagnetic flow metre for liquid velocity profile measurement is an instrument that is highly suited for control via a microcontroller. © 2013 ISA Published by ISA All rights reserved.

In Situ Catalytic Groundwater Treatment Using Palladium Catalysts and Horizontal Flow Treatment Wells

DTIC Science & Technology

2007-06-01

runoff from Drainage Area B. Potentially contaminated surface runoff from Drainage Area B may enter the soil , and subsequently the groundwater, along...an estimated 250,000 gallons of JP-4 jet fuel were released. Soil was excavated and approximately 100,000 gallons of fuel were recovered during...Monitoring wells (4 wells, $4,000 per well) $16,000 Palladium catalyst treatment system $61,000 Palladium catalyst with eggshell coating (20 kg, $245

Control system adds to precipitator efficiency

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

Gurrole, G.

1978-02-01

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

Heat And Mass Transfer Analysis of a Film Evaporative MEMS Tunable Array

NASA Astrophysics Data System (ADS)

O'Neill, William J.

This thesis details the heat and mass transfer analysis of a MEMs microthruster designed to provide propulsive, attitude control and thermal control capabilities to a cubesat. This thruster is designed to function by retaining water as a propellant and applying resistive heating in order to increase the temperature of the liquid-vapor interface to either increase evaporation or induce boiling to regulate mass flow. The resulting vapor is then expanded out of a diverging nozzle to produce thrust. Because of the low operating pressure and small length scale of this thruster, unique forms of mass transfer analysis such as non-continuum gas flow were modeled using the Direct Simulation Monte Carlo method. Continuum fluid/thermal simulations using COMSOL Multiphysics have been applied to model heat and mass transfer in the solid and liquid portions of the thruster. The two methods were coupled through variables at the liquid-vapor interface and solved iteratively by the bisection method. The simulations presented in this thesis confirm the thermal valving concept. It is shown that when power is applied to the thruster there is a nearly linear increase in mass flow and thrust. Thus, mass flow can be regulated by regulating the applied power. This concept can also be used as a thermal control device for spacecraft.

Modeling and measuring non-Newtonian shear flows of soft interfaces

NASA Astrophysics Data System (ADS)

Lopez, Juan; Raghunandan, Aditya; Underhill, Patrick; Hirsa, Amir

2017-11-01

Soft interfaces of polymers, particles, and proteins between fluid phases are ubiquitous in industrial and natural processes. The flow response of such systems to deformation is often not linear, as one would expect for Newtonian interfaces. The resistance to (pure shear) flow of interfaces is generally characterized by a single intrinsic material property, the surface shear viscosity. Predicted shear responses of Newtonian interfaces have achieved consensus across a wide range of flow conditions and measurement devices, when the nonlinear hydrodynamic coupling to the bulk phase is correctly accounted for. However, predicting the flows of sheared non-Newtonian interfaces remains a challenge. Here, we introduce a computational model that incorporates a non-Newtonian constitutive equation for the sheared interface and properly accounts for the coupled interfacial and bulk phase flows. We compare predictions to experiments performed with a model phospholipid system, DPPC - the main constituent of mammalian lung surfactant. Densely packed films of DPPC are directly sheared in a knife-edge surface viscometer. Yield-stress and shear thinning behaviors are shown to be accurately captured across hydrodynamic regimes straddling the Stokes flow limit to inertia dominated flows. Supported by NASA Grant NNX13AQ22G.

Nickel L-edge and K-edge X-ray absorption spectroscopy of non-innocent Ni[S₂C₂(CF₃)₂]₂(n) series (n = -2, -1, 0): direct probe of nickel fractional oxidation state changes.

PubMed

Gu, Weiwei; Wang, Hongxin; Wang, Kun

2014-05-07

A series of nickel dithiolene complexes Ni[S2C2(CF3)2]2(n) (n = -2, -1, 0) has been investigated using Ni L- and K-edge X-ray absorption spectroscopy (XAS). The L3 centroid shifts about 0.3 eV for a change of one unit in the formal oxidation state (or 0.3 eV per oxi), corresponding to ~33% of the shift for Ni oxides or fluorides (about 0.9 eV per oxi). The K-edge XAS edge position shifts about 0.7 eV per oxi, corresponding to ~38% of that for Ni oxides (1.85 eV per oxi). In addition, Ni L sum rule analysis found the Ni(3d) ionicity in the frontier orbitals being 50.5%, 44.0% and 38.5% respectively (for n = -2, -1, 0), in comparison with their formal oxidation states (of Ni(II), Ni(III), and Ni(IV)). For the first time, direct and quantitative measurement of the Ni fractional oxidation state changes becomes possible for Ni dithiolene complexes, illustrating the power of L-edge XAS and L sum rule analysis in such a study. The Ni L-edge and K-edge XAS can be used in a complementary manner to better assess the oxidation states for Ni.

L-Edge X-ray Absorption Spectroscopic Investigation of {FeNO} 6: Delocalization vs Antiferromagnetic Coupling

DOE PAGES

Yan, James J.; Gonzales, Margarita A.; Mascharak, Pradip K.; ...

2016-12-22

NO is a classic non-innocent ligand, and iron nitrosyls can have different electronic structure descriptions depending on their spin state and coordination environment. These highly covalent ligands are found in metalloproteins and are also used as models for Fe–O 2 systems. Here, this study utilizes iron L-edge X-ray absorption spectroscopy (XAS), interpreted using a valence bond configuration interaction multiplet model, to directly experimentally probe the electronic structure of the S = 0 {FeNO} 6 compound [Fe(PaPy 3)NO] 2+ (PaPy 3 = N,N-bis(2-pyridylmethyl)amine-N-ethyl-2-pyridine-2-carboxamide) and the S = 0 [Fe(PaPy 3)CO] + reference compound. This method allows separation of the σ-donation andmore » π-acceptor interactions of the ligand through ligand-to-metal and metal-to-ligand charge-transfer mixing pathways. The analysis shows that the {FeNO} 6 electronic structure is best described as Fe III–NO(neutral), with no localized electron in an NO π* orbital or electron hole in an Fe dπ orbital. This delocalization comes from the large energy gap between the Fe–NO π-bonding and antibonding molecular orbitals relative to the exchange interactions between electrons in these orbitals. This study demonstrates the utility of L-edge XAS in experimentally defining highly delocalized electronic structures.« less

Investigation of the Influence of Heat Balance Shifts on the Freeze Microstructure and Composition in Aluminum Smelting Bath System: Cryolite-CaF2-AlF3-Al2O3

NASA Astrophysics Data System (ADS)

Liu, Jingjing; Fallah-Mehrjardi, Ata; Shishin, Denis; Jak, Evgueni; Dorreen, Mark; Taylor, Mark

2017-12-01

In an aluminum electrolysis cell, the side ledge forms on side walls to protect it from the corrosive cryolitic bath. In this study, a series of laboratory analogue experiments have been carried out to investigate the microstructure and composition of side ledge (freeze linings) at different heat balance steady states. Three distinct layers are found in the freeze linings formed in the designed Cryolite-CaF2-AlF3-Al2O3 electrolyte system: a closed (columnar) crystalline layer, an open crystalline layer, and a sealing layer. This layered structure changes when the heat balance is shifted between different steady states, by melting or freezing the open crystalline layer. Phase chemistry of the freeze lining is studied in this paper to understand the side ledge formation process upon heat balance shifts. Electron probe X-ray microanalysis (EPMA) is used to characterize the microstructure and compositions of distinct phases existing in the freeze linings, which are identified as cryolite, chiolite, Ca-cryolite, and alumina. A freeze formation mechanism is further developed based on these microstructural/compositional investigations and also thermodynamic calculations through the software—FactSage. It is found that entrapped liquid channels exist in the open crystalline layer, assisting with the mass transfer between solidified crystals and bulk molten bath.

Graphene as a thin-film catalyst booster: graphene-catalyst interface plays a critical role.

PubMed

Chae, Sieun; Jin Choi, Won; Sang Chae, Soo; Jang, Seunghun; Chang, Hyunju; Lee, Tae Il; Kim, Youn Sang; Lee, Jeong-O

2017-12-08

Due to its extreme thinness, graphene can transmit some surface properties of its underlying substrate, a phenomenon referred to as graphene transparency. Here we demonstrate the application of the transparency of graphene as a protector of thin-film catalysts and a booster of their catalytic efficiency. The photocatalytic degradation of dye molecules by ZnO thin films was chosen as a model system. A ZnO thin film coated with monolayer graphene showed greater catalytic efficiency and long-term stability than did bare ZnO. Interestingly, we found the catalytic efficiency of the graphene-coated ZnO thin film to depend critically on the nature of the bottom ZnO layer; graphene transferred to a relatively rough, sputter-coated ZnO thin film showed rather poor catalytic degradation of the dye molecules while a smooth sol-gel-synthesized ZnO covered with monolayer graphene showed enhanced catalytic degradation. Based on a systematic investigation of the interface between graphene and ZnO thin films, we concluded the transparency of graphene to be critically dependent on its interface with a supporting substrate. Graphene supported on an atomically flat substrate was found to efficiently transmit the properties of the substrate, but graphene suspended on a substrate with a rough nanoscale topography was completely opaque to the substrate properties. Our experimental observations revealed the morphology of the substrate to be a key factor affecting the transparency of graphene, and should be taken into account in order to optimally apply graphene as a protector of catalytic thin films and a booster of their catalysis.

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

Tao, Franklin

Two main categories of heterogeneous catalysts are metal and metal oxide which catalyze 80% chemical reactions at solid-gas and solid-liquid interfaces. Metal oxide catalysts are much more complicated than metal catalysts. The reason is that the cations of the metal atoms could exhibit a few different oxidation states on surface of the same catalyst particle such as Co 3O 4 or change of their oxidation states under different reactive environments. For a metal catalyst, there is only one oxidation state typically. In addition, surface of a metal oxide can be terminated with multiple surface functionalities including O atoms with differentmore » binding configurations and OH group. For metal, only metal atoms are exposed typically. Obviously, the complication of surface chemistry and structure of a metal oxide makes studies of surface of an oxide catalyst very challenging. Due to the complication of surface of a meal oxide, the electronic and geometric structures of surface of a metal oxide and the exposed species have received enormous attention since oxide catalysts catalyze at least 1/3 chemical reactions in chemical and energy industries. Understanding of catalytic reactions on early transition metal oxide-based catalysts is fundamentally intriguing and of great practical interest in energy- and environment-related catalysis. Exploration of surface chemistry of oxide-based catalysts at molecular level during catalysis has remained challenging though it is critical in deeply understanding catalysis on oxide-based catalysts and developing oxide-based catalysts with high activity and selectivity. Thus, the overall objective of this project is to explore surface chemistry and structure of early transition metal oxide-based catalysts through in-situ characterization of surface of catalysts, measurements of catalytic performances, and then build an intrinsic correlation of surface chemistry and structure with their catalytic performances in a few important catalytic reactions, and essentially fundamentally understand catalytic mechanism. Furthermore, this correlation will guide the design of catalysts with high activity and selectivity.« less

Promoted Iron Nanocrystals Obtained via Ligand Exchange as Active and Selective Catalysts for Synthesis Gas Conversion

PubMed Central

2017-01-01

Colloidal synthesis routes have been recently used to fabricate heterogeneous catalysts with more controllable and homogeneous properties. Herein a method was developed to modify the surface composition of colloidal nanocrystal catalysts and to purposely introduce specific atoms via ligands and change the catalyst reactivity. Organic ligands adsorbed on the surface of iron oxide catalysts were exchanged with inorganic species such as Na2S, not only to provide an active surface but also to introduce controlled amounts of Na and S acting as promoters for the catalytic process. The catalyst composition was optimized for the Fischer–Tropsch direct conversion of synthesis gas into lower olefins. At industrially relevant conditions, these nanocrystal-based catalysts with controlled composition were more active, selective, and stable than catalysts with similar composition but synthesized using conventional methods, possibly due to their homogeneity of properties and synergic interaction of iron and promoters. PMID:28824820

Catalysts and method

DOEpatents

Taylor, Charles E.; Noceti, Richard P.

1991-01-01

An improved catlayst and method for the oxyhydrochlorination of methane is disclosed. The catalyst includes a pyrogenic porous support on which is layered as active material, cobalt chloride in major proportion, and minor proportions of an alkali metal chloride and of a rare earth chloride. On contact of the catalyst with a gas flow of methane, HC1 and oxygen, more than 60% of the methane is converted and of that converted more than 40% occurs as monochloromethane. Advantageously, the monochloromethane can be used to produce gasoline boiling range hydrocarbons with the recycle of HCl for further reaction. This catalyst is also of value for the production of formic acid as are analogous catalysts with lead, silver or nickel chlorides substituted for the cobalt chloride.

Electrochemical Catalyst-Support Effects and Their Stabilizing Role for IrOx Nanoparticle Catalysts during the Oxygen Evolution Reaction.

PubMed

Oh, Hyung-Suk; Nong, Hong Nhan; Reier, Tobias; Bergmann, Arno; Gliech, Manuel; Ferreira de Araújo, Jorge; Willinger, Elena; Schlögl, Robert; Teschner, Detre; Strasser, Peter

2016-09-28

Redox-active support materials can help reduce the noble-metal loading of a solid chemical catalyst while offering electronic catalyst-support interactions beneficial for catalyst durability. This is well known in heterogeneous gas-phase catalysis but much less discussed for electrocatalysis at electrified liquid-solid interfaces. Here, we demonstrate experimental evidence for electronic catalyst-support interactions in electrochemical environments and study their role and contribution to the corrosion stability of catalyst/support couples. Electrochemically oxidized Ir oxide nanoparticles, supported on high surface area carbons and oxides, were selected as model catalyst/support systems for the electrocatalytic oxygen evolution reaction (OER). First, the electronic, chemical, and structural state of the catalyst/support couple was compared using XANES, EXAFS, TEM, and depth-resolved XPS. While carbon-supported oxidized Ir particle showed exclusively the redox state (+4), the Ir/IrOx/ATO system exhibited evidence of metal/metal-oxide support interactions (MMOSI) that stabilized the metal particles on antimony-doped tin oxide (ATO) in sustained lower Ir oxidation states (Ir(3.2+)). At the same time, the growth of higher valent Ir oxide layers that compromise catalyst stability was suppressed. Then the electrochemical stability and the charge-transfer kinetics of the electrocatalysts were evaluated under constant current and constant potential conditions, where the analysis of the metal dissolution confirmed that the ATO support mitigates Ir(z+) dissolution thanks to a stronger MMOSI effect. Our findings raise the possibility that MMOSI effects in electrochemistry-largely neglected in the past-may be more important for a detailed understanding of the durability of oxide-supported nanoparticle OER catalysts than previously thought.

A Programmable System for Motion Control

NASA Technical Reports Server (NTRS)

Nowlin, Brent C.

2003-01-01

The need for improved flow measurements in the flow path of aeronautics testing facilities has led the NASA Glenn Research Center to develop a new motion control system. The new system is programmable, offering a flexibility unheard of in previous systems. The motion control system is PLC-based, which leads to highly accurate positioning ability, as well as reliability. The user interface is a software-based HMI package, which also adds flexibility to the overall system. The system also has the ability to create and execute motion profiles. This paper discusses the system's operation, control implementation, and experiences.

Modifying ceria (111) with a TiO2 nanocluster for enhanced reactivity.

PubMed

Nolan, Michael

2013-11-14

Modification of ceria catalysts is of great interest for oxidation reactions such as oxidative dehydrogenation of alcohols. Improving the reactivity of ceria based catalysts for these reactions means that they can be run at lower temperatures and density functional theory (DFT) simulations of new structures and compositions are proving valuable in the development of these catalysts. In this paper, we have used DFT+U (DFT corrected for on-site Coulomb interactions) to examine the reactivity of a novel modification of ceria, namely, modifying with TiO2, using the example of a Ti2O4 species adsorbed on the ceria (111) surface. The oxygen vacancy formation energy in the Ti2O4-CeO2 system is significantly reduced over the bare ceria surfaces, which together with previous work on ceria-titania indicates that the presence of the interface favours oxygen vacancy formation. The energy gain upon hydrogenation of the catalyst, which is the rate determining step in oxidative dehydrogenation, further points to the improved oxidation power of this catalyst structure.

Gold-supported cerium-doped NiO x catalysts for water oxidation

DOE PAGES

Ng, Jia Wei Desmond; García-Melchor, Max; Bajdich, Michal; ...

2016-04-29

Here, the development of high-performance catalysts for the oxygen-evolution reaction (OER) is paramount for cost-effective conversion of renewable electricity to fuels and chemicals. Here we report the significant enhancement of the OER activity of electrodeposited NiO x films resulting from the combined effects of using cerium as a dopant and gold as a metal support. This NiCeO x–Au catalyst delivers high OER activity in alkaline media, and is among the most active OER electrocatalysts yet reported. On the basis of experimental observations and theoretical modelling, we ascribe the activity to a combination of electronic, geometric and support effects, where highlymore » active under-coordinated sites at the oxide support interface are modified by the local chemical binding environment and by doping the host Ni oxide with Ce. The NiCeO x–Au catalyst is further demonstrated in a device context by pairing it with a nickel–molybdenum hydrogen evolution catalyst in a water electrolyser, which delivers 50 mA consistently at 1.5 V over 24 h of continuous operation.« less