Catalytic silica particles via template-directed molecular imprinting

Energy Technology Data Exchange (ETDEWEB)

Markowitz, M.A.; Kust, P.R.; Deng, G.; Schoen, P.E.; Dordick, J.S.; Clark, D.S.; Gaber, B.P.

2000-02-22

The surfaces of silica particle were molecularly imprinted with an {alpha}-chymotrypsin transition-state analogue (TSA) by utilizing the technique of template-directed synthesis of mineralized materials. The resulting catalytic particles hydrolyzed amides in an enantioselective manner. A mixture of a nonionic surfactant and the acylated chymotrysin TSA, with the TSA acting as the headgroup at the surfactant-water interface, was used to form a microemulsion for silica particle formation. Incorporation of amine-, dihydroimidazole-, and carboxylate-terminated trialkoxysilanes into the particles during imprinting resulted in enhancement of the rates of amide hydrolysis. Acylated imprint molecules formed more effective imprints in the presence of the functionalized silanes than nonacylated imprint molecules. Particles surface-imprinted with the chymotrypsin TSA were selective for the trypsin substrate, and particles surface-imprinted with the L-isomer of the enzyme TSA were enantioselective for the D-isomer of the substrate.

Pyroelectrically Induced Pyro-Electro-Chemical Catalytic Activity of BaTiO3 Nanofibers under Room-Temperature Cold–Hot Cycle Excitations

Directory of Open Access Journals (Sweden)

Yuntao Xia

2017-04-01

Full Text Available A pyro-electro-chemical catalytic dye decomposition using lead-free BaTiO3 nanofibers was realized under room-temperature cold–hot cycle excitation (30–47 °C with a high Rhodamine B (RhB decomposition efficiency ~99%, which should be ascribed to the product of pyro-electric effect and electrochemical redox reaction. Furthermore, the existence of intermediate product of hydroxyl radical in pyro-electro-chemical catalytic process was also observed. There is no significant decrease in pyro-electro-chemical catalysis activity after being recycled five times. The pyro-electrically induced pyro-electro-chemical catalysis provides a high-efficient, reusable and environmentally friendly technology to remove organic pollutants from water.

Reversible switching of fluorophore property based on intrinsic conformational transition of adenylate kinase during its catalytic cycle.

Science.gov (United States)

Fujii, Akira; Hirota, Shun; Matsuo, Takashi

2013-07-17

Adenylate kinase shows a conformational transition (OPEN and CLOSED forms) during substrate binding and product release to mediate the phosphoryl transfer between ADP and ATP/AMP. The protein motional characteristics will be useful to construct switching systems of fluorophore properties caused by the catalytic cycle of the enzyme. This paper demonstrates in situ reversible switching of a fluorophore property driven by the conformational transition of the enzyme. The pyrene-conjugated mutant adenylate kinase is able to switch the monomer/excimer emission property of pyrene on addition of ADP or P(1)P(5)-di(adenosine-5')pentaphosphate (Ap5A, a transition state analog). The observation under the dilute condition (~0.1 μM) indicates that the emission spectral change was caused by the motion of a protein molecule and not led by protein-protein interactions through π-π stacking of pyrene rings. The switching can be reversibly conducted by using hexokinase-coupling reaction. The fashion of the changes in emission intensities at various ligand concentrations is different between ADP, Mg(2+)-bound ADP, and Mg(2+)-bound Ap5A. The emission property switching is repeatable by a sequential addition of a substrate in a one-pot process. It is proposed that the property of a synthetic molecule on the enzyme surface is switchable in response to the catalytic cycle of adenylate kinase.

Catalytic CO Oxidation over Au Nanoparticles Loaded Nanoporous Nickel Phosphate Composite

Directory of Open Access Journals (Sweden)

Xiaonan Leng

2015-01-01

Full Text Available Au/nickel phosphate-5 (Au/VSB-5 composite with the noble metal loading amount of 1.43 wt.% is prepared by using microporous VSB-5 nanocrystals as the support. Carbon monoxide (CO oxidation reaction is carried out over the sample with several catalytic cycles. Complete conversion of CO is achieved at 238°C over the catalyst at the first catalytic cycle. The catalytic activity improved greatly at the second cycle with the complete conversion fulfilled at 198°C and preserved for the other cycles. A series of experiments such as X-ray diffraction (XRD, high resolution transmission electron microscopy (HRTEM, ultraviolet-visible (UV-vis spectroscopy, and X-ray photoelectron spectroscopy (XPS are carried out to characterize the catalysts before and after the reaction to study the factors influencing this promotion at the second cycle.

Direct catalytic cross-coupling of organolithium compounds

NARCIS (Netherlands)

Giannerini, Massimo; Fananas Mastral, Martin; Feringa, Ben L.

Catalytic carbon-carbon bond formation based on cross-coupling reactions plays a central role in the production of natural products, pharmaceuticals, agrochemicals and organic materials. Coupling reactions of a variety of organometallic reagents and organic halides have changed the face of modern

Controlled synthesis of graphitic carbon-encapsulated α-Fe2O3 nanocomposite via low-temperature catalytic graphitization of biomass and its lithium storage property

International Nuclear Information System (INIS)

Wu, Feng; Huang, Rong; Mu, Daobin; Wu, Borong; Chen, Yongjian

2016-01-01

Highlights: • Facile synthesis of graphitic carbon/α-Fe 2 O 3 nano-sized anode composite. • In situ low temperature catalytic graphitization of biomass material. • Onion-like graphitic carbon layers conformally encapsulating around α-Fe 2 O 3 core. • High lithium storage properties, especially, outstanding cycle performance. - Abstract: A delicate structure of graphitic carbon-encapsulated α-Fe 2 O 3 nanocomposite is in situ constructed via “Absorption–Catalytic graphitization–Oxidation” strategy, taking use of biomass matter of degreasing cotton as carbon precursor and solution reservoir. With the assistance of the catalytic graphitization effect of iron core, onion-like graphitic carbon (GC) shell is made directly from the biomass at low temperature (650 °C). The nanosized α-Fe 2 O 3 particles would effectively mitigate volumetric strain and shorten Li + transport path during charge/discharge process. The graphitic carbon shells may promote charge transfer and protect active particles from directly exposing to electrolyte to maintain interfacial stability. As a result, the as-prepared α-Fe 2 O 3 @GC composite displays an outstanding cycle performance with a reversible capacity of 1070 mA h g −1 after 430 cycles at 0.2C, as well as a good rate capability of ∼ 950 mA h g −1 after 100 cycles at 1C and ∼ 850 mA h g −1 even up to 200 cycles at a 2C rate.

Kinetic-quantum chemical model for catalytic cycles: the Haber-Bosch process and the effect of reagent concentration.

Science.gov (United States)

Kozuch, Sebastian; Shaik, Sason

2008-07-03

A combined kinetic-quantum chemical model is developed with the goal of estimating in a straightforward way the turnover frequency (TOF) of catalytic cycles, based on the state energies obtained by quantum chemical calculations. We describe how the apparent activation energy of the whole cycle, so-called energetic span (delta E), is influenced by the energy levels of two species: the TOF determining transition state (TDTS) and the TOF determining intermediate (TDI). Because these key species need not be adjoining states, we conclude that for catalysis there are no rate-determining steps, only rate determining states. In addition, we add here the influence of reactants concentrations. And, finally, the model is applied to the Haber-Bosch process of ammonia synthesis, for which we show how to calculate which catalyst will be the most effective under specific reagents conditions.

Catalytic Combustion of Gasified Waste

Energy Technology Data Exchange (ETDEWEB)

Kusar, Henrik

2003-09-01

This thesis concerns catalytic combustion for gas turbine application using a low heating-value (LHV) gas, derived from gasified waste. The main research in catalytic combustion focuses on methane as fuel, but an increasing interest is directed towards catalytic combustion of LHV fuels. This thesis shows that it is possible to catalytically combust a LHV gas and to oxidize fuel-bound nitrogen (NH{sub 3}) directly into N{sub 2} without forming NO{sub x} The first part of the thesis gives a background to the system. It defines waste, shortly describes gasification and more thoroughly catalytic combustion. The second part of the present thesis, paper I, concerns the development and testing of potential catalysts for catalytic combustion of LHV gases. The objective of this work was to investigate the possibility to use a stable metal oxide instead of noble metals as ignition catalyst and at the same time reduce the formation of NO{sub x} In paper II pilot-scale tests were carried out to prove the potential of catalytic combustion using real gasified waste and to compare with the results obtained in laboratory scale using a synthetic gas simulating gasified waste. In paper III, selective catalytic oxidation for decreasing the NO{sub x} formation from fuel-bound nitrogen was examined using two different approaches: fuel-lean and fuel-rich conditions. Finally, the last part of the thesis deals with deactivation of catalysts. The various deactivation processes which may affect high-temperature catalytic combustion are reviewed in paper IV. In paper V the poisoning effect of low amounts of sulfur was studied; various metal oxides as well as supported palladium and platinum catalysts were used as catalysts for combustion of a synthetic gas. In conclusion, with the results obtained in this thesis it would be possible to compose a working catalytic system for gas turbine application using a LHV gas.

A Simple Catalytic Mechanism for the Direct Coupling of α-Carbonyls with Functionalized Amines: A One-Step Synthesis of Plavix

OpenAIRE

Evans, Ryan W.; Zbieg, Jason R.; Zhu, Shaolin; Li, Wei; MacMillan, David W. C.

2013-01-01

The direct α-amination of ketones, esters, and aldehydes has been accomplished via copper catalysis. In the presence of catalytic copper(II) bromide, a diverse range of carbonyl and amine substrates undergo fragment coupling to produce synthetically useful α-amino substituted motifs. The transformation is proposed to proceed via a catalytically generated α-bromo carbonyl species; nucleophilic displacement of the bromide by the amine then delivers the α-amino carbonyl adduct while the catalyst...

Directed evolution of a β-mannanase from Rhizomucor miehei to improve catalytic activity in acidic and thermophilic conditions.

Science.gov (United States)

Li, Yan-Xiao; Yi, Ping; Yan, Qiao-Juan; Qin, Zhen; Liu, Xue-Qiang; Jiang, Zheng-Qiang

2017-01-01

β-Mannanase randomly cleaves the β-1,4-linked mannan backbone of hemicellulose, which plays the most important role in the enzymatic degradation of mannan. Although the industrial applications of β-mannanase have tremendously expanded in recent years, the wild-type β-mannanases are still defective for some industries. The glycoside hydrolase (GH) family 5 β-mannanase ( Rm Man5A) from Rhizomucor miehei shows many outstanding properties, such as high specific activity and hydrolysis property. However, owing to the low catalytic activity in acidic and thermophilic conditions, the application of Rm Man5A to the biorefinery of mannan biomasses is severely limited. To overcome the limitation, Rm Man5A was successfully engineered by directed evolution. Through two rounds of screening, a mutated β-mannanase (m Rm Man5A) with high catalytic activity in acidic and thermophilic conditions was obtained, and then characterized. The mutant displayed maximal activity at pH 4.5 and 65 °C, corresponding to acidic shift of 2.5 units in optimal pH and increase by 10 °C in optimal temperature. The catalytic efficiencies ( k cat / K m ) of m Rm Man5A towards many mannan substrates were enhanced more than threefold in acidic and thermophilic conditions. Meanwhile, the high specific activity and excellent hydrolysis property of Rm Man5A were inherited by the mutant m Rm Man5A after directed evolution. According to the result of sequence analysis, three amino acid residues were substituted in m Rm Man5A, namely Tyr233His, Lys264Met, and Asn343Ser. To identify the function of each substitution, four site-directed mutations (Tyr233His, Lys264Met, Asn343Ser, and Tyr233His/Lys264Met) were subsequently generated, and the substitutions at Tyr233 and Lys264 were found to be the main reason for the changes of m Rm Man5A. Through directed evolution of Rm Man5A, two key amino acid residues that controlled its catalytic efficiency under acidic and thermophilic conditions were identified

Theoretical Investigation of the Enzymatic Phosphoryl Transfer of β-phosphoglucomutase: Revisiting Both Steps of the Catalytic Cycle

Energy Technology Data Exchange (ETDEWEB)

Elsasser, Brigitta M.; Dohmeier-Fischer, Silvia; Fels, Gregor

2012-07-12

Enzyme catalyzed phosphate transfer is a part of almost all metabolic processes. Such reactions are of central importance for the energy balance in all organisms and play important roles in cellular control at all levels. Mutases transfer a phosphoryl group while nucleases cleave the phosphodiester linkages between two nucleotides. The subject of our present study is the Lactococcus lactis β-phosphoglucomutase (β-PGM), which effectively catalyzes the interconversion of β-D-glucose-1-phosphate (β-G1P) to β- D-glucose-6-phosphate (β-G6P) and vice versa via stabile intermediate β-D-glucose-1,6-(bis)phosphate (β-G1,6diP) in the presence of Mg2+. In this paper we revisited the reaction mechanism of the phosphoryl transfer starting from the bisphosphate β-G1,6diP in both directions (toward β-G1P and β-G6P) combining docking techniques and QM/MM theoretical method at the DFT/PBE0 level of theory. In addition we performed NEB (nudged elastic band) and free energy calculations to optimize the path and to identify the transition states and the energies involved in the catalytic cycle. Our calculations reveal that both steps proceed via dissociative pentacoordinated phosphorane, which is not a stabile intermediate but rather a transition state. In addition to the Mg2+ ion, Ser114 and Lys145 also play important roles in stabilizing the large negative charge on the phosphate through strong coordination with the phosphate oxygens and guiding the phosphate group throughout the catalytic process. The calculated energy barrier of the reaction for the β-G1P to β-G1,6diP step is only slightly higher than for the β-G1,6diP to β-G6P step (16.10 kcal mol-1 versus 15.10 kcal mol-1) and is in excellent agreement with experimental findings (14.65 kcal mol-1).

Effects of a catalytic volatile particle remover (VPR) on the particulate matter emissions from a direct injection spark ignition engine.

Science.gov (United States)

Xu, Fan; Chen, Longfei; Stone, Richard

2011-10-15

Emissions of fine particles have been shown to have a large impact on the atmospheric environment and human health. Researchers have shown that gasoline engines, especially direct injection spark ignition (DISI) engines, tend to emit large amounts of small size particles compared to diesel engines fitted with diesel particulate filters (DPFs). As a result, the particle number emissions of DISI engines will be restricted by the forthcoming EU6 legislation. The particulate emission level of DISI engines means that they could face some challenges in meeting the EU6 requirement. This paper is an experimental study on the size-resolved particle number emissions from a spray guided DISI engine and the performance of a catalytic volatile particle remover (VPR), as the EU legislation seeks to exclude volatile particles. The performance of the catalytic VPR was evaluated by varying its temperature and the exhaust residence time. The effect of the catalytic VPR acting as an oxidation catalyst on particle emissions was also tested. The results show that the catalytic VPR led to a marked reduction in the number of particles, especially the smaller size (nucleation mode) particles. The catalytic VPR is essentially an oxidation catalyst, and when post three-way catalyst (TWC) exhaust was introduced to the catalytic VPR, the performance of the catalytic VPR was not affected much by the use of additional air, i.e., no significant oxidation of the PM was observed.

Chronic fluoxetine treatment directs energy metabolism towards the citric acid cycle and oxidative phosphorylation in rat hippocampal nonsynaptic mitochondria.

Science.gov (United States)

Filipović, Dragana; Costina, Victor; Perić, Ivana; Stanisavljević, Andrijana; Findeisen, Peter

2017-03-15

Fluoxetine (Flx) is the principal treatment for depression; however, the precise mechanisms of its actions remain elusive. Our aim was to identify protein expression changes within rat hippocampus regulated by chronic Flx treatment versus vehicle-controls using proteomics. Fluoxetine-hydrohloride (15mg/kg) was administered daily to adult male Wistar rats for 3weeks, and cytosolic and nonsynaptic mitochondrial hippocampal proteomes were analyzed. All differentially expressed proteins were functionally annotated according to biological process and molecular function using Uniprot and Blast2GO. Our comparative study revealed that in cytosolic and nonsynaptic mitochondrial fractions, 60 and 3 proteins respectively, were down-regulated, and 23 and 60 proteins, respectively, were up-regulated. Proteins differentially regulated in cytosolic and nonsynaptic mitochondrial fractions were primarily related to cellular and metabolic processes. Of the identified proteins, the expressions of calretinin and parvalbumine were confirmed. The predominant molecular functions of differentially expressed proteins in both cell hippocampal fractions were binding and catalytic activity. Most differentially expressed proteins in nonsynaptic mitochondria were catalytic enzymes involved in the pyruvate metabolism, citric acid cycle, oxidative phosphorylation, ATP synthesis, ATP transduction and glutamate metabolism. Results indicate that chronic Flx treatment may influence proteins involved in calcium signaling, cytoskeletal structure, chaperone system and stimulates energy metabolism via the upregulation of GAPDH expression in cytoplasm, as well as directing energy metabolism toward the citric acid cycle and oxidative phosphorylation in nonsynaptic mitochondria. This approach provides new insight into the chronic effects of Flx treatment on protein expression in a key brain region associated with stress response and memory. Copyright © 2017 Elsevier B.V. All rights reserved.

High-efficiency plasma catalytic removal of dilute benzene from air

International Nuclear Information System (INIS)

Fan, Hong-Yu; Shi, Chuan; Li, Xiao-Song; Zhao, De-Zhi; Xu, Yong; Zhu, Ai-Min

2009-01-01

Achieving complete oxidation, good humidity tolerance and low energy cost is the key issue that needs to be addressed in plasma catalytic volatile organic compounds removal from air. For this purpose, Ag/HZSM-5 catalyst-packed dielectric barrier discharge using a cycled system composed of a storage stage and a discharge stage was studied. For dilute benzene removal from simulated air, Ag/HZSM-5 catalysts exhibit not only preferential adsorption of benzene in humid air at the storage stage but also almost complete oxidation of adsorbed benzene at the discharge stage. Five 'storage-discharge' cycles were examined, which suggests that Ag/HZSM-5 catalysts are very stable during the cycled 'storage-discharge' (CSD) plasma catalytic process. High oxidation rate of absorbed benzene as well as low energy cost can be achieved at a moderate discharge power. In an example of the CSD plasma catalytic remedy of simulated air containing 4.7 ppm benzene with 50% RH and 600 ml min -1 flow rate, the energy cost was as low as 3.7 x 10 -3 kWh m -3 air. This extremely low energy cost to remove low-concentration pollutants from air undoubtedly makes the environmental applications of the plasma catalytic technique practical.

NOx Direct Decomposition: Potentially Enhanced Thermodynamics and Kinetics on Chemically Modified Ferroelectric Surfaces

Science.gov (United States)

Kakekhani, Arvin; Ismail-Beigi, Sohrab

2014-03-01

NOx are regulated pollutants produced during automotive combustion. As part of an effort to design catalysts for NOx decomposition that operate in oxygen rich environment and permit greater fuel efficiency, we study chemistry of NOx on (001) ferroelectric surfaces. Changing the polarization at such surfaces modifies electronic properties and leads to switchable surface chemistry. Using first principles theory, our previous work has shown that addition of catalytic RuO2 monolayer on ferroelectric PbTiO3 surface makes direct decomposition of NO thermodynamically favorable for one polarization. Furthermore, the usual problem of blockage of catalytic sites by strong oxygen binding is overcome by flipping polarization that helps desorb the oxygen. We describe a thermodynamic cycle for direct NO decomposition followed by desorption of N2 and O2. We provide energy barriers and transition states for key steps of the cycle as well as describing their dependence on polarization direction. We end by pointing out how a switchable order parameter of substrate,in this case ferroelectric polarization, allows us to break away from some standard compromises for catalyst design(e.g. the Sabatier principle). This enlarges the set of potentially catalytic metals. Primary support from Toyota Motor Engineering and Manufacturing, North America, Inc.

Studies of Catalytic Model Systems

DEFF Research Database (Denmark)

Holse, Christian

The overall topic of this thesis is within the field of catalysis, were model systems of different complexity have been studied utilizing a multipurpose Ultra High Vacuum chamber (UHV). The thesis falls in two different parts. First a simple model system in the form of a ruthenium single crystal...... of the Cu/ZnO nanoparticles is highly relevant to industrial methanol synthesis for which the direct interaction of Cu and ZnO nanocrystals synergistically boost the catalytic activity. The dynamical behavior of the nanoparticles under reducing and oxidizing environments were studied by means of ex situ X......-ray Photoelectron Electron Spectroscopy (XPS) and in situ Transmission Electron Microscopy (TEM). The surface composition of the nanoparticles changes reversibly as the nanoparticles exposed to cycles of high-pressure oxidation and reduction (200 mbar). Furthermore, the presence of metallic Zn is observed by XPS...

Can cycling safety be improved by opening all unidirectional cycle paths for cycle traffic in both directions? A theoretical examination of available literature and data.

Science.gov (United States)

Methorst, Rob; Schepers, Paul; Kamminga, Jaap; Zeegers, Theo; Fishman, Elliot

2017-08-01

Many studies have found bicycle-motor vehicle crashes to be more likely on bidirectional cycle paths than on unidirectional cycle paths because drivers do not expect cyclists riding at the right side of the road. In this paper we discuss the hypothesis that opening all unidirectional cycle paths for cycle traffic in both directions prevent this lack of expectancy and accordingly improves cycling safety. A new national standard requires careful consideration because a reversal is difficult once cyclists are used to their new freedom of route choice. We therefore explored the hypothesis using available data, research, and theories. The results show that of the length of cycle paths along distributor roads in the Netherlands, 72% is bidirectional. If drivers would become used to cyclists riding at the left side of the road, this result raises the question of why bidirectional cycle paths in the Netherlands still have a poor safety record compared to unidirectional cycle paths. Moreover, our exploration suggested that bidirectional cycle paths have additional safety problems. It increases the complexity of unsignalized intersections because drivers have to scan more directions in a short period of time. Moreover, there are some indications that the likelihood of frontal crashes between cyclists increases. We reject the hypothesis that opening all unidirectional cycle paths for cycle traffic in both directions will improve cycle safety. We recommend more attention for mitigating measures given the widespread application of bidirectional cycle paths in the Netherlands. Copyright © 2016 Elsevier Ltd. All rights reserved.

Catalytic Cycle of Haloalkane Dehalogenases Toward Unnatural Substrates Explored by Computational Modeling.

Science.gov (United States)

Marques, Sérgio M; Dunajova, Zuzana; Prokop, Zbynek; Chaloupkova, Radka; Brezovsky, Jan; Damborsky, Jiri

2017-08-28

The anthropogenic toxic compound 1,2,3-trichloropropane is poorly degradable by natural enzymes. We have previously constructed the haloalkane dehalogenase DhaA31 by focused directed evolution ( Pavlova, M. et al. Nat. Chem. Biol. 2009 , 5 , 727 - 733 ), which is 32 times more active than the wild-type enzyme and is currently the most active variant known against that substrate. Recent evidence has shown that the structural basis responsible for the higher activity of DhaA31 was poorly understood. Here we have undertaken a comprehensive computational study of the main steps involved in the biocatalytic hydrolysis of 1,2,3-trichloropropane to decipher the structural basis for such enhancements. Using molecular dynamics and quantum mechanics approaches we have surveyed (i) the substrate binding, (ii) the formation of the reactive complex, (iii) the chemical step, and (iv) the release of the products. We showed that the binding of the substrate and its transport through the molecular tunnel to the active site is a relatively fast process. The cleavage of the carbon-halogen bond was previously identified as the rate-limiting step in the wild-type. Here we demonstrate that this step was enhanced in DhaA31 due to a significantly higher number of reactive configurations of the substrate and a decrease of the energy barrier to the S N 2 reaction. C176Y and V245F were identified as the key mutations responsible for most of those improvements. The release of the alcohol product was found to be the rate-limiting step in DhaA31 primarily due to the C176Y mutation. Mutational dissection of DhaA31 and kinetic analysis of the intermediate mutants confirmed the theoretical observations. Overall, our comprehensive computational approach has unveiled mechanistic details of the catalytic cycle which will enable a balanced design of more efficient enzymes. This approach is applicable to deepen the biochemical knowledge of a large number of other systems and may contribute to robust

Method of fabricating a catalytic structure

Science.gov (United States)

Rollins, Harry W [Idaho Falls, ID; Petkovic, Lucia M [Idaho Falls, ID; Ginosar, Daniel M [Idaho Falls, ID

2009-09-22

A precursor to a catalytic structure comprising zinc oxide and copper oxide. The zinc oxide has a sheet-like morphology or a spherical morphology and the copper oxide comprises particles of copper oxide. The copper oxide is reduced to copper, producing the catalytic structure. The catalytic structure is fabricated by a hydrothermal process. A reaction mixture comprising a zinc salt, a copper salt, a hydroxyl ion source, and a structure-directing agent is formed. The reaction mixture is heated under confined volume conditions to produce the precursor. The copper oxide in the precursor is reduced to copper. A method of hydrogenating a carbon oxide using the catalytic structure is also disclosed, as is a system that includes the catalytic structure.

Direct catalytic conversion of brown seaweed-derived alginic acid to furfural using 12-tungstophosphoric acid catalyst in tetrahydrofuran/water co-solvent

International Nuclear Information System (INIS)

Park, Geonu; Jeon, Wonjin; Ban, Chunghyeon; Woo, Hee Chul; Kim, Do Heui

2016-01-01

Highlights: • Furfural was produced by catalytic conversion of macroalgae-derived alginic acid. • 12-Tungstophosphoric acid (H_3PW_1_2O_4_0) showed remarkable catalytic performance. • Tetrahydrofuran (THF) as a reaction medium significantly enhanced production of furfural. - Abstract: Furfural, a biomass-derived platform chemical, was produced by acid-catalyzed reaction of alginic acid extracted from brown seaweed. Three acid catalysts, H_2SO_4, Amberlyst15 and 12-tungstophosphoric acid (H_3PW_1_2O_4_0), were compared to evaluate their catalytic performance for the alginic acid conversion. The H_3PW_1_2O_4_0 catalyst showed the highest catalytic activity, yielding the maximum furfural yield (33.8%) at 180 °C for 30 min in tetrahydrofuran/water co-solvent. Higher reaction temperature promoted the conversion of alginic acid to furfural, but the transformation of furfural to humin was also accelerated. To our knowledge, this is the highest furfural yield among studies about the direct catalytic conversion of alginic acid. Furthermore, products distribution with time-on-stream was investigated in detail, which led us to propose a reaction pathway.

Actual characteristics study on HTR-10GT coupling with direct gas turbine cycle

International Nuclear Information System (INIS)

Peng Xuechuang; Zhu Shutang; Wang Jie

2005-01-01

Compared with a plant of steam turbine cycle, a HTGR plant with direct gas turbine cycle has a higher thermal efficiency. A lot of investigations on the characteristics of HTR-10GT, which is the reactor studying project of Tsinghua University, have been carried out, however, all of them are based on the theoretical Brayton Cycle which neglects many actual conditions, such as leakage, pressure loss and so on. For engineering practices, leakage is an unavoidable problem. The difference of the location and capacity of leakage will directly influence the working medium's thermoparameters and lead to fall of the cycle efficiency. The present study is focused on the performance of an actual Brayton cycle with practical conditions of leakage. The present study which based on building the physical and mathematical model of the leakage, aims to study the actual characteristics of the direct gas turbine circle. (authors)

Mathematical interpretation of Brownian motor model: Limit cycles and directed transport phenomena

Science.gov (United States)

Yang, Jianqiang; Ma, Hong; Zhong, Suchuang

2018-03-01

In this article, we first suggest that the attractor of Brownian motor model is one of the reasons for the directed transport phenomenon of Brownian particle. We take the classical Smoluchowski-Feynman (SF) ratchet model as an example to investigate the relationship between limit cycles and directed transport phenomenon of the Brownian particle. We study the existence and variation rule of limit cycles of SF ratchet model at changing parameters through mathematical methods. The influences of these parameters on the directed transport phenomenon of a Brownian particle are then analyzed through numerical simulations. Reasonable mathematical explanations for the directed transport phenomenon of Brownian particle in SF ratchet model are also formulated on the basis of the existence and variation rule of the limit cycles and numerical simulations. These mathematical explanations provide a theoretical basis for applying these theories in physics, biology, chemistry, and engineering.

Approximating maximum weight cycle covers in directed graphs with weights zero and one

NARCIS (Netherlands)

Bläser, Markus; Manthey, Bodo

2005-01-01

A cycle cover of a graph is a spanning subgraph each node of which is part of exactly one simple cycle. A $k$-cycle cover is a cycle cover where each cycle has length at least $k$. Given a complete directed graph with edge weights zero and one, Max-$k$-DCC(0, 1) is the problem of finding a k-cycle

Dynamic structural change of the self-assembled lanthanum complex induced by lithium triflate for direct catalytic asymmetric aldol-Tishchenko reaction.

Science.gov (United States)

Horiuchi, Yoshihiro; Gnanadesikan, Vijay; Ohshima, Takashi; Masu, Hyuma; Katagiri, Kosuke; Sei, Yoshihisa; Yamaguchi, Kentaro; Shibasaki, Masakatsu

2005-09-05

The development of a direct catalytic asymmetric aldol-Tishchenko reaction and the nature of its catalyst are described. An aldol-Tishchenko reaction of various propiophenone derivatives with aromatic aldehydes was promoted by [LaLi3(binol)3] (LLB), and reactivity and enantioselectivity were dramatically enhanced by the addition of lithium trifluoromethanesulfonate (LiOTf). First, we observed a dynamic structural change of LLB by the addition of LiOTf using 13C NMR spectroscopy, electronspray ionization mass spectrometry (ESI-MS), and cold-spray ionization mass spectrometry (CSI-MS). X-ray crystallography revealed that the structure of the newly generated self-assembled complex was a binuclear [La2Li4(binaphthoxide)5] complex 6. A reverse structural change of complex 6 to LLB by the addition of one equivalent of Li2(binol) was also confirmed by ESI-MS and experimental results. The drastic concentration effects on the direct catalytic asymmetric aldol-Tishchenko reaction suggested that the addition of LiOTf to LLB generated an active oligomeric catalyst species.

Automated Prediction of Catalytic Mechanism and Rate Law Using Graph-Based Reaction Path Sampling.

Science.gov (United States)

Habershon, Scott

2016-04-12

In a recent article [ J. Chem. Phys. 2015 , 143 , 094106 ], we introduced a novel graph-based sampling scheme which can be used to generate chemical reaction paths in many-atom systems in an efficient and highly automated manner. The main goal of this work is to demonstrate how this approach, when combined with direct kinetic modeling, can be used to determine the mechanism and phenomenological rate law of a complex catalytic cycle, namely cobalt-catalyzed hydroformylation of ethene. Our graph-based sampling scheme generates 31 unique chemical products and 32 unique chemical reaction pathways; these sampled structures and reaction paths enable automated construction of a kinetic network model of the catalytic system when combined with density functional theory (DFT) calculations of free energies and resultant transition-state theory rate constants. Direct simulations of this kinetic network across a range of initial reactant concentrations enables determination of both the reaction mechanism and the associated rate law in an automated fashion, without the need for either presupposing a mechanism or making steady-state approximations in kinetic analysis. Most importantly, we find that the reaction mechanism which emerges from these simulations is exactly that originally proposed by Heck and Breslow; furthermore, the simulated rate law is also consistent with previous experimental and computational studies, exhibiting a complex dependence on carbon monoxide pressure. While the inherent errors of using DFT simulations to model chemical reactivity limit the quantitative accuracy of our calculated rates, this work confirms that our automated simulation strategy enables direct analysis of catalytic mechanisms from first principles.

Life Cycle Assessment Applied to Naphtha Catalytic Reforming Analyse de cycle de vie appliquée au reformage catalytique du naphta

Directory of Open Access Journals (Sweden)

Portha J.-F.

2010-10-01

Full Text Available Facing the increase of environmental concerns in the oil and gas industry, engineers and scientists need information to assess sustainability of chemical processes. Among the different methods available, Life Cycle Assessment (LCA is widely used. In this study, LCA is applied to a catalytic reforming process using the Eco- Indicator 99 as life cycle impact assessment method. The main identified environmental impacts are fossil fuels consumption, climate change and respiratory effects due to inorganics compounds. The influence of different process parameters (feed composition, reaction temperature is determined with respect to environmental impacts. Two allocation methods are analysed (mass and exergetic allocation and two different process versions are compared in order to determine the effect of some improvements on environmental impact. Les considérations liées à l’environnement doivent de plus en plus être prises en compte par les ingénieurs et les scientifiques afin de juger de la durabilité des procédés chimiques dans l’industrie pétrolière et gazière. Parmi les différentes méthodes d’analyse environnementale, l’Analyse de Cycle de Vie (ACV est très utilisée. Dans cette étude, l’ACV est appliquée au procédé de reformage catalytique du naphta en utilisant la méthode Eco-Indicateur 99 comme méthode d’analyse des impacts du cycle de vie. Les principaux impacts environnementaux du procédé sont la consommation de combustibles fossiles, le changement climatique et les effets sur la respiration liés aux composés organiques. L’influence de différents paramètres (composition de l’alimentation, température de réaction sur les impacts environnementaux est testée. Deux méthodes d’allocation sont analysées (allocation massique et énergétique et deux versions du procédé de reformage catalytique sont comparées afin de déterminer les améliorations possibles permettant de minimiser les impacts.

Preparation and electrochemistry of Pd-Ni/Si nanowire nanocomposite catalytic anode for direct ethanol fuel cell.

Science.gov (United States)

Miao, Fengjuan; Tao, Bairui; Chu, Paul K

2012-04-28

A new silicon-based anode suitable for direct ethanol fuel cells (DEFCs) is described. Pd-Ni nanoparticles are coated on Si nanowires (SiNWs) by electroless co-plating to form the catalytic materials. The electrocatalytic properties of the SiNWs and ethanol oxidation on the Pd-Ni catalyst (Pd-Ni/SiNWs) are investigated electrochemically. The effects of temperature and working potential limit in the anodic direction on ethanol oxidation are studied by cyclic voltammetry. The Pd-Ni/SiNWs electrode exhibits higher electrocatalytic activity and better long-term stability in an alkaline solution. It also yields a larger current density and negative onset potential thus boding well for its application to fuel cells. This journal is © The Royal Society of Chemistry 2012

Investigation of combustion and thermodynamic performance of a lean burn catalytic combustion gas turbine system

International Nuclear Information System (INIS)

Yin Juan; Weng Yiwu

2011-01-01

The goals of this research were to investigate the combustion and thermodynamic performance of a lean burn catalytic combustion gas turbine. The characteristics of lean burn catalytic combustion were investigated by utilising 1D heterogeneous plug flow model which was validated by experiments. The effects of operating parameters on catalytic combustion were numerically analysed. The system models were built in ASPEN Plus and three independent design variables, i.e. compressor pressure ratio (PR), regenerator effectiveness (RE) and turbine inlet temperature (TIT) were selected to analyse the thermodynamic performance of the thermal cycle. The main results show that: simulations from 1D heterogeneous plug flow model can capture the trend of catalytic combustion and describe the behavior of the catalytic monolith in detail. Inlet temperature is the most significant parameter that impacts operation of the catalytic combustor. When TIT and RE are constant, the increase of PR results in lowering the inlet temperature of the catalytic combustor, which results in decreasing methane conversion. The peak thermal efficiency and the optimal PR at a constant TIT increase with the increase of TIT; and at the constant PR, the thermal efficiency increases with the increase of TIT. However, with lower TIT conditions, the optimal PR and the peak efficiency at a constant TIT of the LBCCGT cycle are relative low to that of the conventional cycle. When TIT and PR are constant, the decrease of RE may result in lower methane conversion. The influences of RE on the methane conversion and the thermal efficiency are more significant at higher PRs. The higher thermal efficiency for the lower RE is achieved at lower PR.

Tree-type values for cycle-free directed graph games

NARCIS (Netherlands)

Khmelnitskaya, Anna Borisovna; Talman, Dolf

2010-01-01

For arbitrary cycle-free directed graph games tree-type values are introduced axiomatically and their explicit formula representation is provided. These values may be considered as natural extensions of the tree and sink values as has been defined correspondingly for rooted and sink forest graph

Forced thermal cycling of catalytic reactions: experiments and modelling

DEFF Research Database (Denmark)

Jensen, Søren; Olsen, Jakob Lind; Thorsteinsson, Sune

2007-01-01

Recent studies of catalytic reactions subjected to fast forced temperature oscillations have revealed a rate enhancement increasing with temperature oscillation frequency. We present detailed studies of the rate enhancement up to frequencies of 2.5 Hz. A maximum in the rate enhancement is observed...... at about 1 Hz. A model for the rate enhancement that includes the surface kinetics and the dynamic partial pressure variations in the reactor is introduced. The model predicts a levelling off of the rate enhancement with frequency at about 1 Hz. The experimentally observed decrease above 1 Hz is explained...

Finding shortest non-trivial cycles in directed graphs on surfaces

Directory of Open Access Journals (Sweden)

Sergio Cabello

2016-04-01

Full Text Available Let $D$ be a weighted directed graph cellularly embedded in a surface of genus $g$, orientable or not, possibly with boundary.  We describe algorithms to compute shortest non-contractible and shortest surface non-separating cycles in $D$, generalizing previous results that dealt with undirected graphs.Our first algorithm computes such cycles in $O(n^2\\log n$ time, where $n$ is the total number of vertices and edges of $D$, thus matching the complexity of the best general algorithm in the undirected case.  It revisits and extends Thomassen's 3-path condition; the technique applies to other families of cycles as well.We also provide more efficient algorithms in special cases, such as graphs with small genus or bounded treewidth, using a divide-and-conquer technique that simplifies the graph while preserving the topological properties of its cycles.  Finally, we give an efficient output-sensitive algorithm, whose running time depends on the length of the shortest non-contractible or non-separating cycle.

DIRECT-CYCLE, BOILING-WATER NUCLEAR REACTOR

Science.gov (United States)

Harrer, J.M.; Fromm, L.W. Jr.; Kolba, V.M.

1962-08-14

A direct-cycle boiling-water nuclear reactor is described that employs a closed vessel and a plurality of fuel assemblies, each comprising an outer tube closed at its lower end, an inner tube, fuel rods in the space between the tubes and within the inner tube. A body of water lying within the pressure vessel and outside the fuel assemblies is converted to saturated steam, which enters each fuel assembly at the top and is converted to superheated steam in the fuel assembly while it is passing therethrough first downward through the space between the inner and outer tubes of the fuel assembly and then upward through the inner tube. (AEC)

Selenoglutathione Diselenide: Unique Redox Reactions in the GPx-Like Catalytic Cycle and Repairing of Disulfide Bonds in Scrambled Protein.

Science.gov (United States)

Shimodaira, Shingo; Asano, Yuki; Arai, Kenta; Iwaoka, Michio

2017-10-24

Selenoglutathione (GSeH) is a selenium analogue of naturally abundant glutathione (GSH). In this study, this water-soluble small tripeptide was synthesized in a high yield (up to 98%) as an oxidized diselenide form, i.e., GSeSeG (1), by liquid-phase peptide synthesis (LPPS). Obtained 1 was applied to the investigation of the glutathione peroxidase (GPx)-like catalytic cycle. The important intermediates, i.e., GSe - and GSeSG, besides GSeO 2 H were characterized by 77 Se NMR spectroscopy. Thiol exchange of GSeSG with various thiols, such as cysteine and dithiothreitol, was found to promote the conversion to GSe - significantly. In addition, disproportionation of GSeSR to 1 and RSSR, which would be initiated by heterolytic cleavage of the Se-S bond and catalyzed by the generated selenolate, was observed. On the basis of these redox behaviors, it was proposed that the heterolytic cleavage of the Se-S bond can be facilitated by the interaction between the Se atom and an amino or aromatic group, which is present at the GPx active site. On the other hand, when a catalytic amount of 1 was reacted with scrambled 4S species of RNase A in the presence of NADPH and glutathione reductase, native protein was efficiently regenerated, suggesting a potential use of 1 to repair misfolded proteins through reduction of the non-native SS bonds.

Catalytic performance improvement of styrene hydrogenation in trickle bed reactor by using periodic operation

International Nuclear Information System (INIS)

Wongkia, Atittahn; Praserthdam, Piyasan; Assabumrungrat, Suttichai; Suriye, Kongkiat; Nonkhamwong, Anuwat

2013-01-01

We investigated the catalytic performance improvement of styrene hydrogenation in a trickle bed reactor by using periodic operation. The effects of cycle period and split on relative conversion, which is defined as styrene conversion obtained from periodic operation over that from steady state operation, were examined at various operating conditions including gas and average liquid flow rates, pressure and temperature. The experimental results reveal that both cycle period and split have strong influence on the catalytic performance. The fast mode (short cycle period) is a favorable condition. The improvement by the periodic operation becomes less pronounced for operations at high average liquid flow rate, pressure and temperature. From this study, a maximum improvement of styrene conversion of 18% is observed

Catalytic performance improvement of styrene hydrogenation in trickle bed reactor by using periodic operation

Energy Technology Data Exchange (ETDEWEB)

Wongkia, Atittahn; Praserthdam, Piyasan; Assabumrungrat, Suttichai [Chulalongkorn University, Bangkok (Thailand); Suriye, Kongkiat; Nonkhamwong, Anuwat [SCG Chemicals Co. Ltd., Bangkok (Thailand)

2013-03-15

We investigated the catalytic performance improvement of styrene hydrogenation in a trickle bed reactor by using periodic operation. The effects of cycle period and split on relative conversion, which is defined as styrene conversion obtained from periodic operation over that from steady state operation, were examined at various operating conditions including gas and average liquid flow rates, pressure and temperature. The experimental results reveal that both cycle period and split have strong influence on the catalytic performance. The fast mode (short cycle period) is a favorable condition. The improvement by the periodic operation becomes less pronounced for operations at high average liquid flow rate, pressure and temperature. From this study, a maximum improvement of styrene conversion of 18% is observed.

CO{sub 2} direct cycles suitable for AGR type reactors; Cycles directs de gaz carbonique applicables aux reacteurs du genre AGR

Energy Technology Data Exchange (ETDEWEB)

Maillet, E [Commissariat a l' Energie Atomique. Centre d' Etudes Nucleaires de Saclay, 91 - Gif-sur-Yvette (France)

1967-10-01

The perspectives given by the gas turbines under pressure, to build simple nuclear power plants and acieving significantly high yield, are specified. The CO{sub 2} is characterised by by good efficiency under moderate temperature (500 to 750 Celsius degrees), compactness and the simpleness of machines and the safe exploitation (supply, storage, relief cooling, thermosyphon). The revision of thermal properties of the CO{sub 2} and loss elements show that several direct cycles would fit in particular to the AGR type reactors. Cycles that would diverge a little from classical models and able to lead to power and heat generation can lead by simple means to the best results. Several satisfying solutions present for the starting up, the power regulation and the stopping. The nuclear power plant components and the functioning safety are equally considered in the present report. The conclusions stimulate the studies and realizations of carbon dioxide gas turbines in when approprite. [French] Les perspectives offertes par la turbine a gaz sous pression, pour construire des centrales nucleaires simples et de rendement progressivement eleve, se precisent actuellement. le CO{sub 2} se distingue par sa bonne efficacite a temperature moderee (500 a 750 degres celsius), la compacite et la simplicite des machines, et la surete qu'il apporte a l'exploitation ( approvisionnement, stockage, refroidissement de secours, thermosiphon). La revision des proprietes thermophysiques du CO{sub 2} et des elements de pertes montre que divers cycles directs conviendraient en particulier aux reacteurs agr ou derives. Des cycles s'ecartant peu des modeles classiques, et se pretant ulterieurement a la production simultanee d'electricite et de chaleur, peuvent conduire par des moyens simples aux meilleurs resultats d'ensemble. Plusieurs solutions satisfaisantes se presentent pour le demarrage, le reglage de la puissance et l'arret. Les composants de la centrale et la surete de fonctionnement sont

Cycling the hot CNO: a teaching methodology

Science.gov (United States)

Frost-Schenk, J. W.; Diget, C. Aa; Bentley, M. A.; Tuff, A.

2018-03-01

An interactive activity to teach the hot Carbon, Nitrogen and Oxygen (HCNO) cycle is proposed. Justification for why the HCNO cycle is important is included via an example of x-ray bursts. The activity allows teaching and demonstration of half-life, nuclear isotopes, nuclear reactions, protons and α-particles, and catalytic processes. Whilst the process example is specific to astrophysics it may be used to teach more broadly about catalytic processes. This practical is designed for use with 10-20 participants, with the intention that the exercise will convey nuclear physics principles in a fun and interactive manner.

Exergy optimization for a novel combination of organic Rankine cycles, Stirling cycle and direct expander turbines

Science.gov (United States)

Moghimi, Mahdi; Khosravian, Mohammadreza

2018-06-01

In this paper, a novel combination of organic Rankine cycles (ORCs), Stirling cycle and direct expander turbines is modeled and optimized using the genetic algorithm. The Exergy efficiency is considered as an objective function in the genetic algorithm. High efficiency is the main advantage of Stirling cycle, however, it needs nearly isothermal compressor and turbine. Therefore, an argon ORC and a R14 ORC are placed before and after the Striling cycle along with two expander turbines at the end of the line. Each component and cycle of the proposed plant in this article is verified by the previous works available in the literature and good agreement is achieved. The obtained results reveal that 27.98%, 20.86% and 12.90% of the total cold exergy are used by argon ORC, Stirling cycle and R14 ORC, respectively. Therefore, utilization of the Stirling cycle is a good idea for the LNG line cold exergy. The maximum exergy destruction occurs in the heat exchanger after the argon ORC (85.786 kJ/s per one kg/s LNG) due to the wasted cold exergy, which can be used for air conditioning systems in the plant. Finally, it would be shown that the maximum efficiency of the proposed plant is 54.25% and the maximum output power is 355.72 kW.

Exergy optimization for a novel combination of organic Rankine cycles, Stirling cycle and direct expander turbines

Science.gov (United States)

Moghimi, Mahdi; Khosravian, Mohammadreza

2018-01-01

In this paper, a novel combination of organic Rankine cycles (ORCs), Stirling cycle and direct expander turbines is modeled and optimized using the genetic algorithm. The Exergy efficiency is considered as an objective function in the genetic algorithm. High efficiency is the main advantage of Stirling cycle, however, it needs nearly isothermal compressor and turbine. Therefore, an argon ORC and a R14 ORC are placed before and after the Striling cycle along with two expander turbines at the end of the line. Each component and cycle of the proposed plant in this article is verified by the previous works available in the literature and good agreement is achieved. The obtained results reveal that 27.98%, 20.86% and 12.90% of the total cold exergy are used by argon ORC, Stirling cycle and R14 ORC, respectively. Therefore, utilization of the Stirling cycle is a good idea for the LNG line cold exergy. The maximum exergy destruction occurs in the heat exchanger after the argon ORC (85.786 kJ/s per one kg/s LNG) due to the wasted cold exergy, which can be used for air conditioning systems in the plant. Finally, it would be shown that the maximum efficiency of the proposed plant is 54.25% and the maximum output power is 355.72 kW.

On the Structural Context and Identification of Enzyme Catalytic Residues

Directory of Open Access Journals (Sweden)

Yu-Tung Chien

2013-01-01

Full Text Available Enzymes play important roles in most of the biological processes. Although only a small fraction of residues are directly involved in catalytic reactions, these catalytic residues are the most crucial parts in enzymes. The study of the fundamental and unique features of catalytic residues benefits the understanding of enzyme functions and catalytic mechanisms. In this work, we analyze the structural context of catalytic residues based on theoretical and experimental structure flexibility. The results show that catalytic residues have distinct structural features and context. Their neighboring residues, whether sequence or structure neighbors within specific range, are usually structurally more rigid than those of noncatalytic residues. The structural context feature is combined with support vector machine to identify catalytic residues from enzyme structure. The prediction results are better or comparable to those of recent structure-based prediction methods.

Cycle-Based Cluster Variational Method for Direct and Inverse Inference

Science.gov (United States)

Furtlehner, Cyril; Decelle, Aurélien

2016-08-01

Large scale inference problems of practical interest can often be addressed with help of Markov random fields. This requires to solve in principle two related problems: the first one is to find offline the parameters of the MRF from empirical data (inverse problem); the second one (direct problem) is to set up the inference algorithm to make it as precise, robust and efficient as possible. In this work we address both the direct and inverse problem with mean-field methods of statistical physics, going beyond the Bethe approximation and associated belief propagation algorithm. We elaborate on the idea that loop corrections to belief propagation can be dealt with in a systematic way on pairwise Markov random fields, by using the elements of a cycle basis to define regions in a generalized belief propagation setting. For the direct problem, the region graph is specified in such a way as to avoid feed-back loops as much as possible by selecting a minimal cycle basis. Following this line we are led to propose a two-level algorithm, where a belief propagation algorithm is run alternatively at the level of each cycle and at the inter-region level. Next we observe that the inverse problem can be addressed region by region independently, with one small inverse problem per region to be solved. It turns out that each elementary inverse problem on the loop geometry can be solved efficiently. In particular in the random Ising context we propose two complementary methods based respectively on fixed point equations and on a one-parameter log likelihood function minimization. Numerical experiments confirm the effectiveness of this approach both for the direct and inverse MRF inference. Heterogeneous problems of size up to 10^5 are addressed in a reasonable computational time, notably with better convergence properties than ordinary belief propagation.

Hydrophilic Pt nanoflowers: synthesis, crystallographic analysis and catalytic performance.

Science.gov (United States)

Mourdikoudis, Stefanos; Altantzis, Thomas; Liz-Marzán, Luis M; Bals, Sara; Pastoriza-Santos, Isabel; Pérez-Juste, Jorge

2016-05-21

Water-soluble Pt nanoflowers (NFs) were prepared by diethylene glycol-mediated reduction of Pt acetylacetonate (Pt(acac) 2 ) in the presence of polyethylenimine. Advanced electron microscopy analysis showed that the NFs consist of multiple branches with a truncated cubic morphology and different crystallographic orientations. We demonstrate that the nature of the solvent strongly influences the resulting morphology. The catalytic performance of the Pt NFs in 4-nitrophenol reduction was found to be superior to that of other nanoparticle-based catalysts. Additionally, the Pt NFs display good catalytic reusability with no loss of activity after five consecutive cycles.

Catalytic combustion of gasified waste - Experimental part. Final report

Energy Technology Data Exchange (ETDEWEB)

Jaeraas, Sven; Kusar, Henrik [Royal Institute of Technology, Stockholm (Sweden). Chemical Engineering and Technology

2003-08-01

This final report covers the work that has been performed within the project P 10547-2, 'Catalytic combustion of gasified waste - system analysis ORWARE'. This project is part of the research programme 'Energy from Waste' financed by the Swedish National Energy Administration. The project has been carried out at the division of Industrial Ecology and at the division of Chemical Technology at Royal Inst. of Technology. The aim of the project has been to study the potentials for catalytic combustion of gasified waste. The supposed end user of the technique is a smaller community in Sweden with 15,000-20,000 inhabitants. The project contains of two sub projects: an experimental part carried out at Chemical Technology and a system analysis carried out at Industrial Ecology. This report covers the experimental part of the project carried out at Chemical Technology. The aim for the experimental part has been to develop and test catalysts with long life-time and a high performance, to reduce the thermal-NO{sub x} below 5 ppm and to significantly reduce NO{sub x} formed from fuel-bound nitrogen. Different experimental studies have been carried out within the project: a set-up of catalytic materials have been tested over a synthetic mixture of the gasified waste, the influence of sulfur present in the gas stream, NO{sub x} formation from fuel bound nitrogen, kinetic studies of CO and H{sub 2} with and without the presence of water and the effects of adding a co-metal to palladium catalysts Furthermore a novel annular reactor design has been used to carry out experiments for kinetic measurements. Real gasification tests of waste pellets directly coupled to catalytic combustion have successfully been performed. The results obtained from the experiments, both the catalytic combustion and from the gasification, have been possible to use in the system analysis. The aim of the system analysis of catalytic combustion of gasified waste takes into consideration

Performance and Economics of Catalytic Glow Plugs and Shields in Direct Injection Natural Gas Engines for the Next Generation Natural Gas Vehicle Program: Final Report

Energy Technology Data Exchange (ETDEWEB)

Mello, J. P.; Bezaire, D.; Sriramulu, S.; Weber, R.

2003-08-01

Subcontractor report details work done by TIAX and Westport to test and perform cost analysis for catalytic glow plugs and shields for direct-injection natural gas engines for the Next Generation Natural Gas Vehicle Program.

Catalytic Enhancement of Carbon Black and Coal-Fueled Hybrid Direct Carbon Fuel Cells

DEFF Research Database (Denmark)

Deleebeeck, Lisa; Ippolito, Davide; Kammer Hansen, Kent

2015-01-01

, Ce1-xREExO2-δ (REE = Pr, Sm)) and metal oxides (LiMn2O4, Ag2O). Materials showing the highest activity in carbon black (Mn2O3, CeO2, Ce0.6Pr0.4O2-δ, Ag2O) were subsequently tested for catalytic activity toward bituminous coal, as revealed by both I-V-P curves and electrochemical impedance...... spectroscopy (EIS). Catalytic activity was evaluated as a function of various physical characteristics of doped ceria and manganese-based materials....

Actual characteristics study on HTR-10GT coupling with direct gas turbine cycle

International Nuclear Information System (INIS)

Peng Xuechuang; Zhu Shutang; Wang Jie

2005-01-01

HTR-10GT is a testing project coupling the reactor HTR-10 with direct gas turbine cycle. Its thermal cycle can be taken as a closed, recuperated and inter-cooled Brayton cycle. The present study is focused on the thermal cycle performance of HTR-10GT under practical conditions of leakage, pressure losses, etc.. Through thermodynamic analysis, the expression of cycle efficiency for actual thermal cycle is derived. By establishing a physical model with friction loss and leakage, a set of governing equation are constructed based on some reasonable assumptions. The results of actual cycle efficiency have been calculated for different leakage amount at different locations while the effects of leakage under different power level have also been calculated and analyzed. (authors)

Characterization of the catalytic center of the Ebola virus L polymerase.

Science.gov (United States)

Schmidt, Marie Luisa; Hoenen, Thomas

2017-10-01

Ebola virus (EBOV) causes a severe hemorrhagic fever in humans and non-human primates. While no licensed therapeutics are available, recently there has been tremendous progress in developing antivirals. Targeting the ribonucleoprotein complex (RNP) proteins, which facilitate genome replication and transcription, and particularly the polymerase L, is a promising antiviral approach since these processes are essential for the virus life cycle. However, until now little is known about L in terms of its structure and function, and in particular the catalytic center of the RNA-dependent RNA polymerase (RdRp) of L, which is one of the most promising molecular targets, has never been experimentally characterized. Using multiple sequence alignments with other negative sense single-stranded RNA viruses we identified the putative catalytic center of the EBOV RdRp. An L protein with mutations in this center was then generated and characterized using various life cycle modelling systems. These systems are based on minigenomes, i.e. miniature versions of the viral genome, in which the viral genes are exchanged against a reporter gene. When such minigenomes are coexpressed with RNP proteins in mammalian cells, the RNP proteins recognize them as authentic templates for replication and transcription, resulting in reporter activity reflecting these processes. Replication-competent minigenome systems indicated that our L catalytic domain mutant was impaired in genome replication and/or transcription, and by using replication-deficient minigenome systems, as well as a novel RT-qPCR-based genome replication assay, we showed that it indeed no longer supported either of these processes. However, it still showed similar expression to wild-type L, and retained its ability to be incorporated into inclusion bodies, which are the sites of EBOV genome replication. We have experimentally defined the catalytic center of the EBOV RdRp, and thus a promising antiviral target regulating an essential

Characterization of the catalytic center of the Ebola virus L polymerase.

Directory of Open Access Journals (Sweden)

Marie Luisa Schmidt

2017-10-01

Full Text Available Ebola virus (EBOV causes a severe hemorrhagic fever in humans and non-human primates. While no licensed therapeutics are available, recently there has been tremendous progress in developing antivirals. Targeting the ribonucleoprotein complex (RNP proteins, which facilitate genome replication and transcription, and particularly the polymerase L, is a promising antiviral approach since these processes are essential for the virus life cycle. However, until now little is known about L in terms of its structure and function, and in particular the catalytic center of the RNA-dependent RNA polymerase (RdRp of L, which is one of the most promising molecular targets, has never been experimentally characterized.Using multiple sequence alignments with other negative sense single-stranded RNA viruses we identified the putative catalytic center of the EBOV RdRp. An L protein with mutations in this center was then generated and characterized using various life cycle modelling systems. These systems are based on minigenomes, i.e. miniature versions of the viral genome, in which the viral genes are exchanged against a reporter gene. When such minigenomes are coexpressed with RNP proteins in mammalian cells, the RNP proteins recognize them as authentic templates for replication and transcription, resulting in reporter activity reflecting these processes. Replication-competent minigenome systems indicated that our L catalytic domain mutant was impaired in genome replication and/or transcription, and by using replication-deficient minigenome systems, as well as a novel RT-qPCR-based genome replication assay, we showed that it indeed no longer supported either of these processes. However, it still showed similar expression to wild-type L, and retained its ability to be incorporated into inclusion bodies, which are the sites of EBOV genome replication.We have experimentally defined the catalytic center of the EBOV RdRp, and thus a promising antiviral target

Mutations in the catalytic core or the C-terminus of murine leukemia virus (MLV) integrase disrupt virion infectivity and exert diverse effects on reverse transcription

International Nuclear Information System (INIS)

Steinrigl, Adolf; Nosek, Dagmara; Ertl, Reinhard; Guenzburg, Walter H.; Salmons, Brian; Klein, Dieter

2007-01-01

Understanding of the structures and functions of the retroviral integrase (IN), a key enzyme in the viral replication cycle, is essential for developing antiretroviral treatments and facilitating the development of safer gene therapy vehicles. Thus, four MLV IN-mutants were constructed in the context of a retroviral vector system, harbouring either a substitution in the catalytic centre, deletions in the C-terminus, or combinations of both modifications. IN-mutants were tested for their performance in different stages of the viral replication cycle: RNA-packaging; RT-activity; transient and stable infection efficiency; dynamics of reverse transcription and nuclear entry. All mutant vectors packaged viral RNA with wild-type efficiencies and displayed only slight reductions in RT-activity. Deletion of either the IN C-terminus alone, or in addition to part of the catalytic domain exerted contrasting effects on intracellular viral DNA levels, implying that IN influences reverse transcription in more than one direction

Reduction of light cycle oil in catalytic cracking of bitumen-derived crude HGOs through catalyst selection

Energy Technology Data Exchange (ETDEWEB)

Ding, Fuchen; Xu, Chunming [State Key Laboratory of Heavy Oil Processing, China University of Petroleum Beijing, 102200 (China); Ng, Siauw H. [National Centre for Upgrading Technology, 1 Oil Patch Drive, Suite A202, Devon, Alberta (Canada); Yui, Sok [Syncrude Research Centre, 9421-17 Avenue, Edmonton, Alberta (Canada)

2007-09-15

In an attempt to reduce the production of light cycle oil (LCO), a non-premium fluid catalytic cracking (FCC) product in North America, a large-pore catalyst containing rare-earth-exchanged Y (REY) zeolite, was used to crack two Canadian bitumen-derived crude heavy gas oils (HGOs) hydrotreated to different extents. For comparison, a regular equilibrium FCC catalyst with ultra-stable Y (USY) zeolite and a conventional western Canadian crude HGO were also included in the study. Cracking experiments were conducted in a fixed-bed microactivity test (MAT) reactor at 510 C, 30 s oil injection time, and varying catalyst-to-oil ratios for different conversions. The results show that pre-cracking of heavy molecules with wide-pore matrix, followed by zeolite cracking, enhanced conversion at the expense of light and heavy cycle oils at a constant catalyst-to-oil ratio, giving improved product selectivities (e.g., higher gasoline and lower dry gas, LCO, and coke yields, in general, at a given conversion). To systematically assess the benefits of employing the specialty catalyst over the regular catalyst in cracking Canadian HGOs, individual product yields were compared at common bases, including constant catalyst-to-oil ratios, conversions, and coke yields for three feeds, and at maximum gasoline yield for one feed. In most cases, the preferred choice of large-pore zeolite-rich catalyst over its counterpart was evident. The observed cracking phenomena were explained based on properties of catalysts and characterization data of feedstocks, including their hydrocarbon type analyses by gas chromatograph with a mass-selective detector (GC-MSD). (author)

Direct cycle type nuclear power plant

International Nuclear Information System (INIS)

Tagawa, Hisato; Ibe, Hidefumi.

1990-01-01

In a direct cycle type nuclear power plant such as BWR type reactor, since oxygen atoms in reactor water are actuvated by neutron irradiation in the reactor core, carry over of the thus formed radioactive nitrogen atoms causes increase in the dosage in a turbine system. Since 16 N accompanies in the main steams in the chemical form of 16 NO, it can not effectively be removed in a nitrogen removing device. In view of the above, hydrogen atom concentration is reduced by adding metals having high reaction with hydrogen atoms, for example, silver ions, chromium ions, or ruthenium ions are added to reactor water. Then, equilibrium concentration of 16 NO in water is reduced by suppressing the reaction: 16 NO 2 + H → 16 NO + OH. (T.M.)

Key Feature of the Catalytic Cycle of TNF-α Converting Enzyme Involves Communication Between Distal Protein Sites and the Enzyme Catalytic Core

International Nuclear Information System (INIS)

Solomon, A.; Akabayov, B.; Frenkel, A.; Millas, M.; Sagi, I.

2007-01-01

Despite their key roles in many normal and pathological processes, the molecular details by which zinc-dependent proteases hydrolyze their physiological substrates remain elusive. Advanced theoretical analyses have suggested reaction models for which there is limited and controversial experimental evidence. Here we report the structure, chemistry and lifetime of transient metal-protein reaction intermediates evolving during the substrate turnover reaction of a metalloproteinase, the tumor necrosis factor-α converting enzyme (TACE). TACE controls multiple signal transduction pathways through the proteolytic release of the extracellular domain of a host of membrane-bound factors and receptors. Using stopped-flow x-ray spectroscopy methods together with transient kinetic analyses, we demonstrate that TACE's catalytic zinc ion undergoes dynamic charge transitions before substrate binding to the metal ion. This indicates previously undescribed communication pathways taking place between distal protein sites and the enzyme catalytic core. The observed charge transitions are synchronized with distinct phases in the reaction kinetics and changes in metal coordination chemistry mediated by the binding of the peptide substrate to the catalytic metal ion and product release. Here we report key local charge transitions critical for proteolysis as well as long sought evidence for the proposed reaction model of peptide hydrolysis. This study provides a general approach for gaining critical insights into the molecular basis of substrate recognition and turnover by zinc metalloproteinases that may be used for drug design

Complete determination of the Pin1 catalytic domain thermodynamic cycle by NMR lineshape analysis

International Nuclear Information System (INIS)

Greenwood, Alexander I.; Rogals, Monique J.; De, Soumya; Lu, Kun Ping; Kovrigin, Evgenii L.; Nicholson, Linda K.

2011-01-01

The phosphorylation-specific peptidyl-prolyl isomerase Pin1 catalyzes the isomerization of the peptide bond preceding a proline residue between cis and trans isomers. To best understand the mechanisms of Pin1 regulation, rigorous enzymatic assays of isomerization are required. However, most measures of isomerase activity require significant constraints on substrate sequence and only yield rate constants for the cis isomer, k cat cis and apparent Michaelis constants, K M App . By contrast, NMR lineshape analysis is a powerful tool for determining microscopic rates and populations of each state in a complex binding scheme. The isolated catalytic domain of Pin1 was employed as a first step towards elucidating the reaction scheme of the full-length enzyme. A 24-residue phosphopeptide derived from the amyloid precurser protein intracellular domain (AICD) phosphorylated at Thr668 served as a biologically-relevant Pin1 substrate. Specific 13 C labeling at the Pin1-targeted proline residue provided multiple reporters sensitive to individual isomer binding and on-enzyme catalysis. We have performed titration experiments and employed lineshape analysis of phosphopeptide 13 C– 1 H constant time HSQC spectra to determine k cat cis , k cat trans , K D cis , and K D trans for the catalytic domain of Pin1 acting on this AICD substrate. The on-enzyme equilibrium value of [E·trans]/[E·cis] = 3.9 suggests that the catalytic domain of Pin1 is optimized to operate on this substrate near equilibrium in the cellular context. This highlights the power of lineshape analysis for determining the microscopic parameters of enzyme catalysis, and demonstrates the feasibility of future studies of Pin1-PPIase mutants to gain insights on the catalytic mechanism of this important enzyme.

Catalytic Wastewater Treatment Using Pillared Clays

Science.gov (United States)

Perathoner, Siglinda; Centi, Gabriele

After introduction on the use of solid catalysts in wastewater treatment technologies, particularly advanced oxidation processes (AOPs), this review discussed the use of pillared clay (PILC) materials in three applications: (i) wet air catalytic oxidation (WACO), (ii) wet hydrogen peroxide catalytic oxidation (WHPCO) on Cu-PILC and Fe-PILC, and (iii) behavior of Ti-PILC and Fe-PILC in the photocatalytic or photo-Fenton conversion of pollutants. Literature data are critically analyzed to evidence the main direction to further investigate, in particularly with reference to the possible practical application of these technologies to treat industrial, municipal, or agro-food production wastewater.

Vapor-Driven Propulsion of Catalytic Micromotors

Science.gov (United States)

Dong, Renfeng; Li, Jinxing; Rozen, Isaac; Ezhilan, Barath; Xu, Tailin; Christianson, Caleb; Gao, Wei; Saintillan, David; Ren, Biye; Wang, Joseph

2015-08-01

Chemically-powered micromotors offer exciting opportunities in diverse fields, including therapeutic delivery, environmental remediation, and nanoscale manufacturing. However, these nanovehicles require direct addition of high concentration of chemical fuel to the motor solution for their propulsion. We report the efficient vapor-powered propulsion of catalytic micromotors without direct addition of fuel to the micromotor solution. Diffusion of hydrazine vapor from the surrounding atmosphere into the sample solution is instead used to trigger rapid movement of iridium-gold Janus microsphere motors. Such operation creates a new type of remotely-triggered and powered catalytic micro/nanomotors that are responsive to their surrounding environment. This new propulsion mechanism is accompanied by unique phenomena, such as the distinct off-on response to the presence of fuel in the surrounding atmosphere, and spatio-temporal dependence of the motor speed borne out of the concentration gradient evolution within the motor solution. The relationship between the motor speed and the variables affecting the fuel concentration distribution is examined using a theoretical model for hydrazine transport, which is in turn used to explain the observed phenomena. The vapor-powered catalytic micro/nanomotors offer new opportunities in gas sensing, threat detection, and environmental monitoring, and open the door for a new class of environmentally-triggered micromotors.

Catalytic Activity Control via Crossover between Two Different Microstructures

KAUST Repository

Zhou, Yuheng

2017-09-08

Metal nanocatalysts hold great promise for a wide range of heterogeneous catalytic reactions, while the optimization strategy of catalytic activity is largely restricted by particle size or shape control. Here, we demonstrate that a reversible microstructural control through the crossover between multiply-twinned nanoparticle (MTP) and single crystal (SC) can be readily achieved by solvent post-treatment on gold nanoparticles (AuNPs). Polar solvents (e.g. water, methanol) direct the transformation from MTP to SC accompanied by the disappearance of twinning and stacking faults. A reverse transformation from SC to MTP is achieved in non-polar solvent (e.g. toluene) mixed with thiol ligands. The transformation between two different microstructures is directly observed by in-situ TEM and leads to a drastic modulation of catalytic activity towards the gas-phase selective oxidation of alcohols. There is a quasi-linear relationship between TOFs and MTP concentrations. Based on the combined experimental and theoretical investigations of alcohol chemisorption on these nanocatalysts, we propose that the exposure of {211}-like microfacets associated with twin boundaries and stack faults accounts for the strong chemisorption of alcohol molecules on MTP AuNPs and thus the exceptionally high catalytic activity.

Highly Dense Isolated Metal Atom Catalytic Sites

DEFF Research Database (Denmark)

Chen, Yaxin; Kasama, Takeshi; Huang, Zhiwei

2015-01-01

-ray diffraction. A combination of electron microscopy images with X-ray absorption spectra demonstrated that the silver atoms were anchored on five-fold oxygen-terminated cavities on the surface of the support to form highly dense isolated metal active sites, leading to excellent reactivity in catalytic oxidation......Atomically dispersed noble-metal catalysts with highly dense active sites are promising materials with which to maximise metal efficiency and to enhance catalytic performance; however, their fabrication remains challenging because metal atoms are prone to sintering, especially at a high metal...... loading. A dynamic process of formation of isolated metal atom catalytic sites on the surface of the support, which was achieved starting from silver nanoparticles by using a thermal surface-mediated diffusion method, was observed directly by using in situ electron microscopy and in situ synchrotron X...

Cycling the Hot CNO: A Teaching Methodology

Science.gov (United States)

Frost-Schenk, J. W.; Diget, C. Aa.; Bentley, M. A.; Tuff, A.

2018-01-01

An interactive activity to teach the hot Carbon, Nitrogen and Oxygen (HCNO) cycle is proposed. Justification for why the HCNO cycle is important is included via an example of x-ray bursts. The activity allows teaching and demonstration of half-life, nuclear isotopes, nuclear reactions, protons and a-particles, and catalytic processes. Whilst the…

Processing and structural characterization of porous reforming catalytic films

International Nuclear Information System (INIS)

Hou Xianghui; Williams, Jey; Choy, Kwang-Leong

2006-01-01

Nickel-based catalysts are often used to reform methanol into hydrogen. The preparation and installation of these catalysts are costly and laborious. As an alternative, directly applying catalytic films onto the separator components can improve the manufacturing efficiency. This paper reports the successful deposition of adherent porous NiO-Al 2 O 3 -based catalytic films with well-controlled stoichiometry, using a single-step Aerosol Assisted Chemical Vapour Deposition (AACVD) method. The microstructure, composition and crystalline phase of the as-deposited catalytic films are characterized using a combination of X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and Fourier Transform Infrared (FTIR) Spectrometer. The results have demonstrated the capability of AACVD to produce porous NiO-Al 2 O 3 -based catalytic films

Redox non-innocent ligands: versatile new tools to control catalytic reactions

NARCIS (Netherlands)

Lyaskovskyy, V.; de Bruin, B.

2012-01-01

In this (tutorial overview) perspective we highlight the use of "redox non-innocent" ligands in catalysis. Two main types of reactivity in which the redox non-innocent ligand is involved can be specified: (A) The redox active ligand participates in the catalytic cycle only by accepting/donating

Direct Catalytic Conversion of Cellulose to 5-Hydroxymethylfurfural Using Ionic Liquids

Directory of Open Access Journals (Sweden)

Sanan Eminov

2016-10-01

Full Text Available Cellulose is the single largest component of lignocellulosic biomass and is an attractive feedstock for a wide variety of renewable platform chemicals and biofuels, providing an alternative to petrochemicals and petrofuels. This potential is currently limited by the existing methods of transforming this poorly soluble polymer into useful chemical building blocks, such as 5-hydroxymethylfurfural (HMF. Ionic liquids have been used successfully to separate cellulose from the other components of lignocellulosic biomass and so the use of the same medium for the challenging transformation of cellulose into HMF would be highly attractive for the development of the biorefinery concept. In this report, ionic liquids based on 1-butyl-3-methylimidazolium cations [C4C1im]+ with Lewis basic (X = Cl− and Brønsted acidic (X = HSO4− anions were used to investigate the direct catalytic transformation of cellulose to HMF. Variables probed included the composition of the ionic liquid medium, the metal catalyst, and the reaction conditions (temperature, substrate concentration. Lowering the cellulose loading and optimising the temperature achieved a 58% HMF yield after only one hour at 150 °C using a 7 mol % loading of the CrCl3 catalyst. This compares favourably with current literature procedures requiring much longer reactions times or approaches that are difficult to scale such as microwave irradiation.

Impact of the Valence Charge of Transition Metals on the Cobalt- and Rhodium-Catalyzed Synthesis of Indenamines, Indenols, and Isoquinolinium Salts: A Catalytic Cycle Involving MIII/MV [M = Co, Rh] for [4+2] Annulation.

Science.gov (United States)

Chiou, Mong-Feng; Jayakumar, Jayachandran; Cheng, Chien-Hong; Chuang, Shih-Ching

2018-06-13

Reaction mechanisms for the synthesis of indenamines, indenols, and isoquinolinium salts through cobalt- and rhodium-catalysis were investigated using density functional theory calculations. We found that the valence charge of transition metals dramatically influences the reaction pathways. Catalytic reactions involving lower-oxidation-state transition metals (M I /M III , M = Co and Rh) generally favor a [3+2] cyclization pathway, whereas those involving higher oxidation states (M III /M V ) proceed through a [4+2] cyclization pathway. A catalytic cycle with novel M III /M V as a crucial species was successfully revealed for isoquinolinium salts synthesis, which highly valent M V was not only encountered in the [RhCp*]-catalysis but also in the [CoCp*]-catalysis.

Influence of boron concentration on growth characteristic and electro-catalytic performance of boron-doped diamond electrodes prepared by direct current plasma chemical vapor deposition

International Nuclear Information System (INIS)

Feng Yujie; Lv Jiangwei; Liu Junfeng; Gao Na; Peng Hongyan; Chen Yuqiang

2011-01-01

A series of boron-doped diamond (BDD) electrodes were prepared by direct current plasma chemical vapor deposition (DC-PCVD) with different compositions of CH 4 /H 2 /B(OCH 3 ) 3 gas mixture. A maximum growth rate of 0.65 mg cm -2 h -1 was obtained with CH 4 /H 2 /B(OCH 3 ) 3 radio of 4/190/10 and this growth condition was also a turning point for discharge plasma stability which arose from the addition of B(OCH 3 ) 3 that changed electron energy distribution and influenced the plasma reaction. The surface coating structure and electro-catalytic performance of the BDD electrodes were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, Hall test, and electrochemical measurement and electro-catalytic oxidation in phenol solution. It is suggested that the boron doping level and the thermal stress in the films are the main factors affecting the electro-catalytic characteristics of the electrodes. Low boron doping level with CH 4 /H 2 /B(OCH 3 ) 3 ratio of 4/199/1 decreased the films electrical conductivity and its electro-catalytic activity. When the carrier concentration in the films reached around 10 20 cm -3 with CH 4 /H 2 /B(OCH 3 ) 3 ratio over a range of 4/195/5-4/185/15, the thermal stress in the films was the key reason that influenced the electro-catalytic activity of the electrodes for its effect on diamond lattice expansion. Therefore, the BDD electrode with modest CH 4 /H 2 /B(OCH 3 ) 3 ratio of 4/190/10 possessed the best phenol removal efficiency.

Integration between direct steam generation in linear solar collectors and supercritical carbon dioxide Brayton power cycles

OpenAIRE

Coco Enríquez, Luis; Muñoz Antón, Javier; Martínez-Val Peñalosa, José María

2015-01-01

Direct Steam Generation in Parabolic Troughs or Linear Fresnel solar collectors is a technology under development since beginning of nineties (1990's) for replacing thermal oils and molten salts as heat transfer fluids in concentrated solar power plants, avoiding environmental impacts. In parallel to the direct steam generation technology development, supercritical Carbon Dioxide Brayton power cycles are maturing as an alternative to traditional Rankine cycles for increasing net plant efficie...

Sinusoidal potential cycling operation of a direct ethanol fuel cell to improving carbon dioxide yields

Science.gov (United States)

Majidi, Pasha; Pickup, Peter G.

2014-12-01

A direct ethanol fuel cell has been operated under sinusoidal (AC) potential cycling conditions in order to increase the yield of carbon dioxide and thereby increase cell efficiency relative to operation at a fixed potential. At 80 °C, faradaic yields of CO2 as high as 25% have been achieved with a PtRu anode catalyst, while the maximum CO2 production at constant potential was 13%. The increased yields under cycling conditions have been attributed to periodic oxidative stripping of adsorbed CO. These results will be important in the optimization of operating conditions for direct ethanol fuel cells, where the benefits of potential cycling are projected to increase as catalysts that produce CO2 more efficiently are implemented.

Ni-Catalyzed Dehydrogenative Cross-Coupling: Direct Transformation of Aldehydes to Esters and Amides

Science.gov (United States)

Whittaker, Aaron M.; Dong, Vy M.

2015-01-01

By exploring a new mode of Ni-catalyzed cross-coupling, we have developed a protocol to transform both aromatic and aliphatic aldehydes into either esters or amides directly. The success of this oxidative coupling depends on the appropriate choice of catalyst and organic oxidant, including the use of either α,α,α-trifluoroacetophenone or excess aldehyde. We present mechanistic data that supports a catalytic cycle involving oxidative addition into the aldehyde C–H bond. PMID:25424967

Toward Facilitative Mentoring and Catalytic Interventions

Science.gov (United States)

Smith, Melissa K.; Lewis, Marilyn

2015-01-01

In TESOL teacher mentoring, giving advice can be conceptualized as a continuum, ranging from directive to facilitative feedback. The goal, over time, is to lead toward the facilitative end of the continuum and specifically to catalytic interventions that encourage self-reflection and autonomous learning. This study begins by examining research on…

Oxidation of phosphine by sulfur or selenium involving a catalytic ...

Indian Academy of Sciences (India)

Administrator

P NMR spec- troscopy. Such interconversion with the participation of breaking of bridging copper-µ3-sulfur bond with the formation of new copper–phosphorous bond led to the development of a catalytic cycle using excess. PPh3 and S or Se as the reacting substrates. The turnover number for the oxidation of PPh3 by S ...

Hydrogen production via catalytic processing of renewable feedstocks

International Nuclear Information System (INIS)

Nazim Muradov; Franklyn Smith; Ali T-Raissi

2006-01-01

Landfill gas (LFG) and biogas can potentially become important feedstocks for renewable hydrogen production. The objectives of this work were: (1) to develop a catalytic process for direct reforming of CH 4 -CO 2 gaseous mixture mimicking LFG, (2) perform thermodynamic analysis of the reforming process using AspenPlus chemical process simulator, (3) determine operational conditions for auto-thermal (or thermo-neutral) reforming of a model CH 4 -CO 2 feedstock, and (4) fabricate and test a bench-scale hydrogen production unit. Experimental data obtained from catalytic reformation of the CH 4 -CO 2 and CH 4 -CO 2 -O 2 gaseous mixtures using Ni-catalyst were in a good agreement with the simulation results. It was demonstrated that catalytic reforming of LFG-mimicking gas produced hydrogen with the purity of 99.9 vol.%. (authors)

Direct versus indirect effects of tropospheric humidity changes on the hydrologic cycle

International Nuclear Information System (INIS)

Sherwood, S C

2010-01-01

Abundant evidence indicates that tropospheric specific humidity increases in a warmer atmosphere, at rates roughly comparable to those at constant relative humidity. While the implications for the planetary energy budget and global warming are well recognized, it is the net atmospheric cooling (or surface heating) that controls the hydrologic cycle. Relative humidity influences this directly through gas-phase radiative transfer, and indirectly by affecting cloud cover (and its radiative effects) and convective heating. Simple calculations show that the two indirect impacts are larger than the direct impact by roughly one and two orders of magnitude respectively. Global or regional relative humidity changes could therefore have significant indirect impacts on energy and water cycles, especially by altering deep convection, even if they are too small to significantly affect global temperature. Studies of climate change should place greater emphasis on these indirect links, which may not be adequately represented in models.

Synthesis, Characterization, and Catalytic Activity of Pd(II Salen-Functionalized Mesoporous Silica

Directory of Open Access Journals (Sweden)

Rotcharin Sawisai

2017-01-01

Full Text Available Salen ligand synthesized from 2-hydroxybenzaldehyde and 2-hydroxy-1-naphthaldehyde was used as a palladium chelating ligand for the immobilization of the catalytic site. Mesoporous silica supported palladium catalysts were prepared by immobilizing Pd(OAc2 onto a mesoporous silica gel through the coordination of the imine-functionalized mesoporous silica gel. The prepared catalysts were characterized by X-ray diffraction (XRD, scanning electron microscopy (SEM, energy dispersive X-ray (EDX, inductivity couple plasma (ICP, nitrogen adsorption-desorption, and Fourier transform infrared (FT-IR spectroscopy. The solid catalysts showed higher activity for the hydroamination of C-(tetra-O-acetyl-β-D-galactopyranosylallene with aromatic amines compared with the corresponding homogenous catalyst. The heterogeneous catalytic system can be easily recovered by simple filtration and reused for up to five cycles with no significant loss of catalytic activity.

Study on the reactive transient α-λ3-iodanyl-acetophenone complex in the iodine(III)/PhI(I) catalytic cycle of iodobenzene-catalyzed α-acetoxylation reaction of acetophenone by electrospray ionization tandem mass spectrometry.

Science.gov (United States)

Wang, Hao-Yang; Zhou, Juan; Guo, Yin-Long

2012-03-30

Hypervalent iodine compounds are important and widely used oxidants in organic chemistry. In 2005, Ochiai reported the PhI-catalyzed α-acetoxylation reaction of acetophenone by the oxidation of PhI with m-chloroperbenzoic acid (m-CPBA) in acetic acid. However, until now, the most critical reactive α-λ(3)-iodine alkyl acetophenone intermediate (3) had not been isolated or directly detected. Electrospray ionization tandem mass spectrometry (ESI-MS/MS) was used to intercept and characterize the transient reactive α-λ(3)-iodine alkyl acetophenone intermediate in the reaction solution. The trivalent iodine species was detected when PhI and m-CPBA in acetic acid were mixed, which indicated the facile oxidation of a catalytic amount of PhI(I) to the iodine(III) species by m-CPBA. Most importantly, 3·H(+) was observed at m/z 383 from the reaction solution and this ion gave the protonated α-acetoxylation product 4·H(+) at m/z 179 in MS/MS by an intramolecular reductive elimination of PhI. These ESI-MS/MS studies showed the existence of the reactive α-λ(3)-iodine alkyl acetophenone intermediate 3 in the catalytic cycle. Moreover, the gas-phase reactivity of 3·H(+) was consistent with the proposed solution-phase reactivity of the α-λ(3)-iodine alkyl acetophenone intermediate 3, thus confirming the reaction mechanism proposed by Ochiai. Copyright © 2012 John Wiley & Sons, Ltd.

Chemically-modified cellulose paper as a microstructured catalytic reactor.

Science.gov (United States)

Koga, Hirotaka; Kitaoka, Takuya; Isogai, Akira

2015-01-15

We discuss the successful use of chemically-modified cellulose paper as a microstructured catalytic reactor for the production of useful chemicals. The chemical modification of cellulose paper was achieved using a silane-coupling technique. Amine-modified paper was directly used as a base catalyst for the Knoevenagel condensation reaction. Methacrylate-modified paper was used for the immobilization of lipase and then in nonaqueous transesterification processes. These catalytic paper materials offer high reaction efficiencies and have excellent practical properties. We suggest that the paper-specific interconnected microstructure with pulp fiber networks provides fast mixing of the reactants and efficient transport of the reactants to the catalytically-active sites. This concept is expected to be a promising route to green and sustainable chemistry.

Chemically-Modified Cellulose Paper as a Microstructured Catalytic Reactor

Directory of Open Access Journals (Sweden)

Hirotaka Koga

2015-01-01

Full Text Available We discuss the successful use of chemically-modified cellulose paper as a microstructured catalytic reactor for the production of useful chemicals. The chemical modification of cellulose paper was achieved using a silane-coupling technique. Amine-modified paper was directly used as a base catalyst for the Knoevenagel condensation reaction. Methacrylate-modified paper was used for the immobilization of lipase and then in nonaqueous transesterification processes. These catalytic paper materials offer high reaction efficiencies and have excellent practical properties. We suggest that the paper-specific interconnected microstructure with pulp fiber networks provides fast mixing of the reactants and efficient transport of the reactants to the catalytically-active sites. This concept is expected to be a promising route to green and sustainable chemistry.

Advanced byproduct recovery: Direct catalytic reduction of sulfur dioxide to elemental sulfur. Quarterly report, April 1--June 30, 1997

Energy Technology Data Exchange (ETDEWEB)

NONE

1997-12-31

The team of Arthur D. Little, Tufts University and Engelhard Corporation are conducting Phase 1 of a four and a half year, two-phase effort to develop and scale-up an advanced byproduct recovery technology that is a direct, single-stage, catalytic process for converting sulfur dioxide to elemental sulfur. This catalytic process reduces SO{sub 2} over a fluorite-type oxide (such as ceria and zirconia). The catalytic activity can be significantly promoted by active transition metals, such as copper. More than 95% elemental sulfur yield, corresponding to almost complete sulfur dioxide conversion, was obtained over a Cu-Ce-O oxide catalyst as part of an on-going DOE-sponsored, University Coal Research Program. This type of mixed metal oxide catalyst has stable activity, high selectivity for sulfur production, and is resistant to water and carbon dioxide poisoning. Tests with CO and CH{sub 4} reducing gases indicate that the catalyst has the potential for flexibility with regard to the composition of the reducing gas, making it attractive for utility use. The performance of the catalyst is consistently good over a range of SO{sub 2} inlet concentration (0.1 to 10%) indicating its flexibility in treating SO{sub 2} tail gases as well as high concentration streams. The principal objective of the Phase 1 program is to identify and evaluate the performance of a catalyst which is robust and flexible with regard to choice of reducing gas. In order to achieve this goal, the authors have planned a structured program including: Market/process/cost/evaluation; Lab-scale catalyst preparation/optimization studies; Lab-scale, bulk/supported catalyst kinetic studies; Bench-scale catalyst/process studies; and Utility review. Progress is reported from all three organizations.

Advanced-ORIENT cycle, its scientific progress and prospect for engineering feasibility

International Nuclear Information System (INIS)

Koyama, Shin-ichi; Yamagishi, Isao; Fujii, Yasuhiko; Suzuki, Tatsuya; Ozawa, Masaki; Fujita, Reiko; Okada, Ken; Tatenuma, Katsuyoshi; Mimura, Hitoshi

2011-01-01

For the ultimate minimization of the ecological risks originated in nuclear fuel recycling, a new fuel cycle paradigm was proposed and the basic researches have been carried out as a first phase under the Adv.-ORIENT (Advanced Optimization by Recycling Instructive Elements) Cycle project. In this paradigm, effective separation of actinide (An) and long lived-fission product (LLFP), transmutation of An, utilization of separated nuclides, such as lanthanides (Lns) and platinum group metals (PGM), were the main directions. In such directions, tertiary pyridine-type resin (TPR) enabled to separate minor actinide (MA)/Ln and then Am/Cm precisely from spent fuel, provided permitting to use HCl as well as and HNO 3 media. Recovery of very pure Am and Cm products could be done in this phase. The PGM and Tc separation; Catalytic electrolytic extraction (CEE) method could effectively separate the light PGM ,Tc from HCl and HNO 3 media, especially by HCl media. The PGM and Tc utilization; Mixed deposit obtained from the CEE experiments, Ru/Rh/Pd/Tc(Re)-Pt electrodes indicated the highest catalytic reactivity on electrolytic production of hydrogen in an alkali solution. Recovery of Cs from simulated spent fuel solution by silica gel loaded with ammonium molybdophosphate (AMP) was carried out, and the uptake rate achieved more than 90%. Separated Cs is expected to utilize as a heat source element. As basic engineering research efforts, some candidate metals, such as Ta, Nb, Zr and Hastelloy-B (Ni-28Mo), were examined to confirm an anti-corrosive property in wide HCl environment. Gram scale experiment to identify a thermo-chemical stability of TPR and TBP (as a reference) was also performed experimentally, and process safety conditions could be found out for its practical use. In this paper, study for each integrant technology was concluded as first trial of Adv.-ORIENT Cycle project, and the perspective for next phase was proposed. (author)

Improved catalytic properties of halohydrin dehalogenase by modification of the halide-binding site.

Science.gov (United States)

Tang, Lixia; Torres Pazmiño, Daniel E; Fraaije, Marco W; de Jong, René M; Dijkstra, Bauke W; Janssen, Dick B

2005-05-03

Halohydrin dehalogenase (HheC) from Agrobacterium radiobacter AD1 catalyzes the dehalogenation of vicinal haloalcohols by an intramolecular substitution reaction, resulting in the formation of the corresponding epoxide, a halide ion, and a proton. Halide release is rate-limiting during the catalytic cycle of the conversion of (R)-p-nitro-2-bromo-1-phenylethanol by the enzyme. The recent elucidation of the X-ray structure of HheC showed that hydrogen bonds between the OH group of Tyr187 and between the Odelta1 atom of Asn176 and Nepsilon1 atom of Trp249 could play a role in stabilizing the conformation of the halide-binding site. The possibility that these hydrogen bonds are important for halide binding and release was studied using site-directed mutagenesis. Steady-state kinetic studies revealed that mutant Y187F, which has lost both hydrogen bonds, has a higher catalytic activity (k(cat)) with two of the three tested substrates compared to the wild-type enzyme. Mutant W249F also shows an enhanced k(cat) value with these two substrates, as well as a remarkable increase in enantiopreference for (R)-p-nitro-2-bromo-1-phenylethanol. In case of a mutation at position 176 (N176A and N176D), a 1000-fold lower catalytic efficiency (k(cat)/K(m)) was obtained, which is mainly due to an increase of the K(m) value of the enzyme. Pre-steady-state kinetic studies showed that a burst of product formation precedes the steady state, indicating that halide release is still rate-limiting for mutants Y187F and W249F. Stopped-flow fluorescence experiments revealed that the rate of halide release is 5.6-fold higher for the Y187F mutant than for the wild-type enzyme and even higher for the W249F enzyme. Taken together, these results show that the disruption of two hydrogen bonds around the halide-binding site increases the rate of halide release and can enhance the overall catalytic activity of HheC.

Catalytic oligomerization of terminal alkynes promoted by organo-f-complexes

International Nuclear Information System (INIS)

Straub, T.; Haskel, A.; Eisen, M.S.

1995-01-01

Organoactinides of the type Cp* 2 AcMe 2 (Cp*=C 5 Me 5 ; Ac=Th, U) are active catalyst precursors for the oligomerization of terminal alkynes HC triple-bond CR (R=alkyl, aryl, SiMe 3 ). The regioselectivity and the extent of oligomerization strongly depend on the alkyne substituent R, whereas the catalytic reactivity is similar for 1 and 2. In the presence of one of these organoactinides, for example, HCCSiMe 3 regioselectively oligomerizes to the head-to-tail dimer 3 (5%) and the trimer 4 (95%). 1 and 2 react with the terminal alkynes, releasing methane, to the corresponding bisacetylide complexes which are active species and in the catalytic reactions. The bisacetylide complex (η 5 -C 5 Me 5 ) 2 U(CCPh) 2 was identified by proton NMR spectroscopy. Subsequent insertion of alkyne molecules in the actinide-carbon σ-bonds leads to the formation of actinide-alkenyl complexes. The turnover limiting step is the release of the organic oligomer from the actinide-organyl complex. A species of the latter has been spectroscopically characterized in the trimerization reaction of HCCSiMe 3 . In this poster, the catalytic reactivity of the actinide alkyls 1 and 2 with various mono-substituted alkynes as well as the spectroscopic characterization of the key organometallic intermediate complexes in the catalytic cycle and a detailed mechanistic discussion are given

H/D exchange mass spectrometry and statistical coupling analysis reveal a role for allostery in a ferredoxin-dependent bifurcating transhydrogenase catalytic cycle.

Science.gov (United States)

Berry, Luke; Poudel, Saroj; Tokmina-Lukaszewska, Monika; Colman, Daniel R; Nguyen, Diep M N; Schut, Gerrit J; Adams, Michael W W; Peters, John W; Boyd, Eric S; Bothner, Brian

2018-01-01

Recent investigations into ferredoxin-dependent transhydrogenases, a class of enzymes responsible for electron transport, have highlighted the biological importance of flavin-based electron bifurcation (FBEB). FBEB generates biomolecules with very low reduction potential by coupling the oxidation of an electron donor with intermediate potential to the reduction of high and low potential molecules. Bifurcating systems can generate biomolecules with very low reduction potentials, such as reduced ferredoxin (Fd), from species such as NADPH. Metabolic systems that use bifurcation are more efficient and confer a competitive advantage for the organisms that harbor them. Structural models are now available for two NADH-dependent ferredoxin-NADP + oxidoreductase (Nfn) complexes. These models, together with spectroscopic studies, have provided considerable insight into the catalytic process of FBEB. However, much about the mechanism and regulation of these multi-subunit proteins remains unclear. Using hydrogen/deuterium exchange mass spectrometry (HDX-MS) and statistical coupling analysis (SCA), we identified specific pathways of communication within the model FBEB system, Nfn from Pyrococus furiosus, under conditions at each step of the catalytic cycle. HDX-MS revealed evidence for allosteric coupling across protein subunits upon nucleotide and ferredoxin binding. SCA uncovered a network of co-evolving residues that can provide connectivity across the complex. Together, the HDX-MS and SCA data show that protein allostery occurs across the ensemble of iron‑sulfur cofactors and ligand binding sites using specific pathways that connect domains allowing them to function as dynamically coordinated units. Copyright © 2017 Elsevier B.V. All rights reserved.

Solar reforming of methane in a direct absorption catalytic reactor on a parabolic dish. 2: Modeling and analysis

Science.gov (United States)

Skocypec, Russell D.; Hogan, Roy E., Jr.; Muir, James F.

1991-01-01

The catalytically enhanced solar absorption receiver (CAESAR) experiment was conducted to determine the thermal, chemical, and mechanical performance of a commercial-scale, dish-mounted, direct catalytic absorption receiver (DCAR) reactor over a range of steady state and transient (cloud) operating conditions. The focus of the experiment is on global performance such as receiver efficiencies and overall methane conversion; it was not intended to provide data for code validation. A numerical model was previously developed to provide guidance in the design of the absorber. The one-dimensional, planar and steady-state model incorporates, the following energy transfer mechanisms: solar and infrared radiation, heterogeneous chemical reaction, conduction in the solid phase, and convection between the fluid and solid phases. A number of upgrades to the model and improved property values are presented here. Model predictions are shown to bound the experimental axial thermocouple data when experimental uncertainties are included. Global predictions are made using a technique in which the incident solar flux distribution is subdivided into flux contour bands. Model predictions for each band are then spatially integrated to provide global predictions such as reactor efficiencies and methane conversions. Global predictions are shown to compare well with experimental data. Reactor predictions for anticipated operating conditions suggest a further decrease in optical density at the front of the absorber inner disk may be beneficial. The need to conduct code-validation experiments is identified as being essential in improving the confidence in the capability to predict large-scale reactor operation.

Exploration of alternate catalytic mechanisms and optimization strategies for retroaldolase design.

Science.gov (United States)

Bjelic, Sinisa; Kipnis, Yakov; Wang, Ling; Pianowski, Zbigniew; Vorobiev, Sergey; Su, Min; Seetharaman, Jayaraman; Xiao, Rong; Kornhaber, Gregory; Hunt, John F; Tong, Liang; Hilvert, Donald; Baker, David

2014-01-09

Designed retroaldolases have utilized a nucleophilic lysine to promote carbon-carbon bond cleavage of β-hydroxy-ketones via a covalent Schiff base intermediate. Previous computational designs have incorporated a water molecule to facilitate formation and breakdown of the carbinolamine intermediate to give the Schiff base and to function as a general acid/base. Here we investigate an alternative active-site design in which the catalytic water molecule was replaced by the side chain of a glutamic acid. Five out of seven designs expressed solubly and exhibited catalytic efficiencies similar to previously designed retroaldolases for the conversion of 4-hydroxy-4-(6-methoxy-2-naphthyl)-2-butanone to 6-methoxy-2-naphthaldehyde and acetone. After one round of site-directed saturation mutagenesis, improved variants of the two best designs, RA114 and RA117, exhibited among the highest kcat (>10(-3)s(-1)) and kcat/KM (11-25M(-1)s(-1)) values observed for retroaldolase designs prior to comprehensive directed evolution. In both cases, the >10(5)-fold rate accelerations that were achieved are within 1-3 orders of magnitude of the rate enhancements reported for the best catalysts for related reactions, including catalytic antibodies (kcat/kuncat=10(6) to 10(8)) and an extensively evolved computational design (kcat/kuncat>10(7)). The catalytic sites, revealed by X-ray structures of optimized versions of the two active designs, are in close agreement with the design models except for the catalytic lysine in RA114. We further improved the variants by computational remodeling of the loops and yeast display selection for reactivity of the catalytic lysine with a diketone probe, obtaining an additional order of magnitude enhancement in activity with both approaches. © 2013.

Enhancement of the catalytic activity of ferulic acid decarboxylase from Enterobacter sp. Px6-4 through random and site-directed mutagenesis.

Science.gov (United States)

Lee, Hyunji; Park, Jiyoung; Jung, Chaewon; Han, Dongfei; Seo, Jiyoung; Ahn, Joong-Hoon; Chong, Youhoon; Hur, Hor-Gil

2015-11-01

The enzyme ferulic acid decarboxylase (FADase) from Enterobacter sp. Px6-4 catalyzes the decarboxylation reaction of lignin monomers and phenolic compounds such as p-coumaric acid, caffeic acid, and ferulic acid into their corresponding 4-vinyl derivatives, that is, 4-vinylphenol, 4-vinylcatechol, and 4-vinylguaiacol, respectively. Among various ferulic acid decarboxylase enzymes, we chose the FADase from Enterobacter sp. Px6-4, whose crystal structure is known, and produced mutants to enhance its catalytic activity by random and site-directed mutagenesis. After three rounds of sequential mutations, FADase(F95L/D112N/V151I) showed approximately 34-fold higher catalytic activity than wild-type for the production of 4-vinylguaiacol from ferulic acid. Docking analyses suggested that the increased activity of FADase(F95L/D112N/V151I) could be due to formation of compact active site compared with that of the wild-type FADase. Considering the amount of phenolic compounds such as lignin monomers in the biomass components, successfully bioengineered FADase(F95L/D112N/V151I) from Enterobacter sp. Px6-4 could provide an ecofriendly biocatalytic tool for producing diverse styrene derivatives from biomass.

Performance analysis of a Kalina cycle for a central receiver solar thermal power plant with direct steam generation

International Nuclear Information System (INIS)

Modi, Anish; Haglind, Fredrik

2014-01-01

Solar thermal power plants have attracted increasing interest in the past few years – with respect to both the design of the various plant components, and extending the operation hours by employing different types of storage systems. One approach to improve the overall plant efficiency is to use direct steam generation with water/steam as both the heat transfer fluid in the solar receivers and the cycle working fluid. This enables operating the plant with higher turbine inlet temperatures. Available literature suggests that it is feasible to use ammonia-water mixtures at high temperatures without corroding the equipment by using suitable additives with the mixture. The purpose of the study reported here was to investigate if there is any benefit of using a Kalina cycle for a direct steam generation, central receiver solar thermal power plant with high live steam temperature (450 °C) and pressure (over 100 bar). Thermodynamic performance of the Kalina cycle in terms of the plant exergy efficiency was evaluated and compared with a simple Rankine cycle. The rates of exergy destruction for the different components in the two cycles were also calculated and compared. The results suggest that the simple Rankine cycle exhibits better performance than the Kalina cycle when the heat input is only from the solar receiver. However, when using a two-tank molten-salt storage system as the primary source of heat input, the Kalina cycle showed an advantage over the simple Rankine cycle because of about 33 % reduction in the storage requirement. The solar receiver showed the highest rate of exergy destruction for both the cycles. The rates of exergy destruction in other components of the cycles were found to be highly dependent on the amount of recuperation, and the ammonia mass fraction and pressure at the turbine inlet. - Highlights: •Kalina cycle for a central receiver solar thermal power plant with direct steam generation. •Rankine cycle shows better plant exergy

Enhancement in catalytic activity of Aspergillus niger XynB by selective site-directed mutagenesis of active site amino acids.

Science.gov (United States)

Wu, Xiuyun; Tian, Zhennan; Jiang, Xukai; Zhang, Qun; Wang, Lushan

2018-01-01

XynB from Aspergillus niger ATCC1015 (AnXynB) is a mesophilic glycoside hydrolase (GH) family 11 xylanase which holds great potentials in a wide variety of industrial applications. In the present study, the catalytic activity and stability of AnXynB were improved by a combination of computational and experimental approaches. Virtual mutation and molecular dynamics simulations indicated that the introduction of Glu and Asn altered the interaction network at the - 3 subsite. Interestingly, the double mutant S41N/T43E displayed 72% increase in catalytic activity when compared to the wild type (WT). In addition, it also showed a better thermostability than the WT enzyme. Kinetic determination of the T43E and S41N/T43E mutants suggested that the higher xylanase activity is probably due to the increasing binding affinity of enzyme and substrate. Consequently, the enzyme activity and thermostability of AnXynB was both increased by selective site-directed mutagenesis at the - 3 subsite of its active site architecture which provides a good example for a successfully engineered enzyme for potential industrial application. Moreover, the molecular evolution approach adopted in this study led to the design of a library of sequences that captures a meaningful functional diversity in a limited number of protein variants.

A consistent reaction scheme for the selective catalytic reduction of nitrogen oxides with ammonia

DEFF Research Database (Denmark)

Janssens, Ton V.W.; Falsig, Hanne; Lundegaard, Lars Fahl

2015-01-01

For the first time, the standard and fast selective catalytic reduction of NO by NH3 are described in a complete catalytic cycle, that is able to produce the correct stoichiometry, while only allowing adsorption and desorption of stable molecules. The standard SCR reaction is a coupling of the ac...... for standard SCR. Finally, the role of a nitrate/nitrite equilibrium and the possible in uence of Cu dimers and Brønsted sites are discussed, and an explanation is offered as to how a catalyst can be effective for SCR, while being a poor catalyst for NO oxidation to NO2....... spectroscopy (FTIR). A consequence of the reaction scheme is that all intermediates in fast SCR are also part of the standard SCR cycle. The calculated activation energy by density functional theory (DFT) indicates that the oxidation of an NO molecule by O2 to a bidentate nitrate ligand is rate determining...

Cross-catalytic peptide nucleic acid (PNA) replication based on templated ligation

DEFF Research Database (Denmark)

Singhal, Abhishek; Nielsen, Peter E

2014-01-01

We report the first PNA self-replicating system based on template directed cross-catalytic ligation, a process analogous to biological replication. Using two template PNAs and four pentameric precursor PNAs, all four possible carbodiimide assisted amide ligation products were detected...... precursors. Cross-catalytic product formation followed product inhibited kinetics, but approximately two replication rounds were observed. Analogous but less efficient replication was found for a similar tetrameric system. These results demonstrate that simpler nucleobase replication systems than natural...

Electric power generating plant having direct-coupled steam and compressed-air cycles

Science.gov (United States)

Drost, M.K.

1981-01-07

An electric power generating plant is provided with a Compressed Air Energy Storage (CAES) system which is directly coupled to the steam cycle of the generating plant. The CAES system is charged by the steam boiler during off peak hours, and drives a separate generator during peak load hours. The steam boiler load is thereby levelized throughout an operating day.

Electric power generating plant having direct coupled steam and compressed air cycles

Science.gov (United States)

Drost, Monte K.

1982-01-01

An electric power generating plant is provided with a Compressed Air Energy Storage (CAES) system which is directly coupled to the steam cycle of the generating plant. The CAES system is charged by the steam boiler during off peak hours, and drives a separate generator during peak load hours. The steam boiler load is thereby levelized throughout an operating day.

Catalytic effect of additional metallic phases on the hydrogen absorption behavior of a Zr-Based alloy

International Nuclear Information System (INIS)

Ruiz, F; Peretti, H; Castro, E; Real, S; Visitin, A; Triaca, W

2005-01-01

The electrochemical hydrogen absorption of electrodes containing Zr 0 .9Ti 0 .1(Ni 0 .5Mn 0 .25Cr 0 .20V 0 .05) 2 is studied in alkaline media by monitoring the activation and discharge capacity along charge-discharge cycling.The considered alloy is tested in both as melted and annealed condition in order to investigate the catalytic effect of small amounts of micro segregated secondary phases of the Zr-Ni system. Since these catalytic phases are only present in the as melted alloys, tests are also carried out using a composite material elaborated from powders of the annealed alloy with the addition of 18 wt.% of the suspected catalytic phases, melted separately.The hydrogen absorption-desorption behavior for the different cases is discussed and correlated with the metallurgical characterization of the materials.The catalytic effects are studied employing cyclic voltammetry and electrochemical impedance techniques. The results are analyzed in terms of a developed physicochemical model

Organic Rankine cycle - review and research directions in engine applications

Science.gov (United States)

Panesar, Angad

2017-11-01

Waste heat to power conversion using Organic Rankine Cycles (ORC) is expected to play an important role in CO2 reductions from diesel engines. Firstly, a review of automotive ORCs is presented focusing on the pure working fluids, thermal architectures and expanders. The discussion includes, but is not limited to: R245fa, ethanol and water as fluids; series, parallel and cascade as architectures; dry saturated, superheated and supercritical as expansion conditions; and scroll, radial turbine and piston as expansion machines. Secondly, research direction in versatile expander and holistic architecture (NOx + CO2) are proposed. Benefits of using the proposed unconventional approaches are quantified using Ricardo Wave and Aspen HYSYS for diesel engine and ORC modelling. Results indicate that, the implementation of versatile piston expander tolerant to two-phase and using cyclopentane can potentially increase the highway drive cycle power by 8%. Furthermore, holistic architecture offering complete utilisation of charge air and exhaust recirculation heat increased the performance noticeably to 5% of engine power at the design point condition.

Supercritical CO{sub 2} mediated synthesis and catalytic activity of graphene/Pd nanocomposites

Energy Technology Data Exchange (ETDEWEB)

Tang, Lulu [School of Chemical Engineering, Yeungnam University, Gyeongsan, Gyeoungbuk 712-749 (Korea, Republic of); Nguyen, Van Hoa [School of Chemical Engineering, Yeungnam University, Gyeongsan, Gyeoungbuk 712-749 (Korea, Republic of); Department of Chemistry, Nha Trang University, 2 Nguyen Dinh Chieu, Nha Trang (Viet Nam); Shim, Jae-Jin, E-mail: jjshim@yu.ac.kr [School of Chemical Engineering, Yeungnam University, Gyeongsan, Gyeoungbuk 712-749 (Korea, Republic of)

2015-11-15

Highlights: • RGO/Pd composite was efficiently prepared via a facile method in supercritical CO{sub 2}. • Graphene sheets were coated uniformly with Pd nanoparticles with a size of ∼8 nm. • Composites exhibited excellent catalytic activity in the Suzuki reaction even after 10 cycles. - Abstract: Graphene sheets were decorated with palladium nanoparticles using a facile and efficient method in supercritical CO{sub 2}. The nanoparticles were formed on the graphene sheets by the simple hydrogen reduction of palladium(II) hexafluoroacetylacetonate precursor in supercritical CO{sub 2}. The product was characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy. Highly dispersed nanoparticles with various sizes and shapes adhered well to the graphene sheets. The composites showed high catalytic activities for the Suzuki reaction under aqueous and aerobic conditions within 5 min. The effects of the different Pd precursor loadings on the catalytic activities of the composites were also examined.

Performance and life cycle environmental benefits of recycling spent ion exchange brines by catalytic treatment of nitrate.

Science.gov (United States)

Choe, Jong Kwon; Bergquist, Allison M; Jeong, Sangjo; Guest, Jeremy S; Werth, Charles J; Strathmann, Timothy J

2015-09-01

Salt used to make brines for regeneration of ion exchange (IX) resins is the dominant economic and environmental liability of IX treatment systems for nitrate-contaminated drinking water sources. To reduce salt usage, the applicability and environmental benefits of using a catalytic reduction technology to treat nitrate in spent IX brines and enable their reuse for IX resin regeneration were evaluated. Hybrid IX/catalyst systems were designed and life cycle assessment of process consumables are used to set performance targets for the catalyst reactor. Nitrate reduction was measured in a typical spent brine (i.e., 5000 mg/L NO3(-) and 70,000 mg/L NaCl) using bimetallic Pd-In hydrogenation catalysts with variable Pd (0.2-2.5 wt%) and In (0.0125-0.25 wt%) loadings on pelletized activated carbon support (Pd-In/C). The highest activity of 50 mgNO3(-)/(min - g(Pd)) was obtained with a 0.5 wt%Pd-0.1 wt%In/C catalyst. Catalyst longevity was demonstrated by observing no decrease in catalyst activity over more than 60 days in a packed-bed reactor. Based on catalyst activity measured in batch and packed-bed reactors, environmental impacts of hybrid IX/catalyst systems were evaluated for both sequencing-batch and continuous-flow packed-bed reactor designs and environmental impacts of the sequencing-batch hybrid system were found to be 38-81% of those of conventional IX. Major environmental impact contributors other than salt consumption include Pd metal, hydrogen (electron donor), and carbon dioxide (pH buffer). Sensitivity of environmental impacts of the sequencing-batch hybrid reactor system to sulfate and bicarbonate anions indicate the hybrid system is more sustainable than conventional IX when influent water contains reuse cycles. The study showed that hybrid IX/catalyst reactor systems have potential to reduce resource consumption and improve environmental impacts associated with treating nitrate-contaminated water sources. Copyright © 2015 Elsevier Ltd. All rights

Catalytic nanoporous membranes

Science.gov (United States)

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.

SNCR technology for NO sub x reduction in the cement industry. [Selective non-catalytic reduction

Energy Technology Data Exchange (ETDEWEB)

Kupper, D; Brentrup, L [Krupp Polysius AG, Beckum (Germany)

1992-03-01

This article discusses the selective non-catalytic (SNCR) process for reducing nitrogen oxides in exhaust gases from cement plants. Topics covered include operating experience, injection of additives, selection of the additive, operating costs, reduction efficiency of SNCR, capital expenditure, secondary emissions and cycles of ammonium. (UK).

A facile synthesis for cauliflower like CeO2 catalysts from Ce-BTC precursor and their catalytic performance for CO oxidation

Science.gov (United States)

Zhang, Xiaodong; Hou, Fulin; Yang, Yang; Wang, Yuxin; Liu, Ning; Chen, Dan; Yang, Yiqiong

2017-11-01

The paper presents a novel and facile method for preparing cauliflowerlike CeO2 through direct decomposition of cerium based metal-organic framework (MOF) Ce-BTC (BTC = 1,3,5-benzenetricarboxylic acid) straw in air. Several analytical tools such as Scanning electron microscopy (SEM), X-ray diffraction (XRD), Thermogravimetric (TG), N2 adsorption-desorption, Temperature programmed reduction (TPR), Raman, X-ray photoelectron spectroscopic (XPS) and Photoluminescence (PL) have been used to characterize Ce-BTC and CeO2. The Ce-BTC calcined at 500 °C (CeO2-500) maintains the morphology of its template ;Ce-BTC; and forms a special cauliflower-like structure. XRD patterns showed that the catalyst has a perfect CeO2 crystal structure and has a smaller particle size. The prepared CeO2 cauliflowers exhibit excellent catalytic activities, long-term stability, and cycling stability for CO oxidation. The improved catalytic activities could be attributed to porous nanorods of CeO2 cauliflowers, which provide more active sites and oxygen vacancy for CO oxidation.

Gate-to-Gate Life Cycle Assessment for Determining Carbon Footprint of Catalytic Converter Assembly Process

Directory of Open Access Journals (Sweden)

A. N. Mustfizul Karim

2017-03-01

Full Text Available With the pursuit of embracing the circular economy, having upward trend in vehicle sales and environmental concern, sustainability has become an imperative part of the global automotive manufacturing strategies. One of the tactics to achieve this sustainable goal is to conserve and enhance the resource base by salvaging the embedded values from end-of-life product and for which, the remanufacturing can be considered as one of the most prominent epitome. Even though many of the auto parts like engine, transmissions, starters, alternators and etc. have been assessed for remanufacturability since last few decades, being a major component of a car body the Catalytic Converter (CC still remains unfocused in literature. However, to examine the remanufacturability of CC, a comprehensive study for assessing its economic, social, and environmental impact is inevitable. Therefore, with an underlying aim of designing the remanufacturable CC, in this endeavour an attempt has made to evaluate the environmental impact of its welding operations by means of energy consumption through gate-to-gate life cycle assessment. Real life data are collected from a Local Malaysian CC manufacturer. The obtained results show that the welding section has a carbon footprint of 0.203 kgCO2e/unit with major emission coming from the plasma arc welding. In addition to that, it is also observed that the value of carbon footprint is not only sensitive to the emission factor and processing time, but also it is responsive to the nature of the processing operations. Certainly, this observation will motivate to change the product design from the prospect of remanufacturing.

Catalytic Conversion of Biomass to Fuels and Chemicals Using Ionic Liquids

Energy Technology Data Exchange (ETDEWEB)

Liu, Wei; Zheng, Richard; Brown, Heather; Li, Joanne; Holladay, John; Cooper, Alan; Rao, Tony

2012-04-13

This project provides critical innovations and fundamental understandings that enable development of an economically-viable process for catalytic conversion of biomass (sugar) to 5-hydroxymethylfurfural (HMF). A low-cost ionic liquid (Cyphos 106) is discovered for fast conversion of fructose into HMF under moderate reaction conditions without any catalyst. HMF yield from fructose is almost 100% on the carbon molar basis. Adsorbent materials and adsorption process are invented and demonstrated for separation of 99% pure HMF product and recovery of the ionic liquid from the reaction mixtures. The adsorbent material appears very stable in repeated adsorption/regeneration cycles. Novel membrane-coated adsorbent particles are made and demonstrated to achieve excellent adsorption separation performances at low pressure drops. This is very important for a practical adsorption process because ionic liquids are known of high viscosity. Nearly 100% conversion (or dissolution) of cellulose in the catalytic ionic liquid into small molecules was observed. It is promising to produce HMF, sugars and other fermentable species directly from cellulose feedstock. However, several gaps were identified and could not be resolved in this project. Reaction and separation tests at larger scales are needed to minimize impacts of incidental errors on the mass balance and to show 99.9% ionic liquid recovery. The cellulose reaction tests were troubled with poor reproducibility. Further studies on cellulose conversion in ionic liquids under better controlled conditions are necessary to delineate reaction products, dissolution kinetics, effects of mass and heat transfer in the reactor on conversion, and separation of final reaction mixtures.

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

Science.gov (United States)

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.

Degradation of paracetamol by catalytic wet air oxidation and sequential adsorption – Catalytic wet air oxidation on activated carbons

International Nuclear Information System (INIS)

Quesada-Peñate, I.; Julcour-Lebigue, C.; Jáuregui-Haza, U.J.; Wilhelm, A.M.; Delmas, H.

2012-01-01

Highlights: ► Three activated carbons (AC) compared as adsorbents and oxidation catalysts. ► Similar evolution for catalytic and adsorptive properties of AC over reuses. ► Acidic and mesoporous AC to be preferred, despite lower initial efficiency. ► Oxidative degradation of paracetamol improves biodegradability. ► Convenient hybrid adsorption–regenerative oxidation process for continuous treatment. - Abstract: The concern about the fate of pharmaceutical products has raised owing to the increasing contamination of rivers, lakes and groundwater. The aim of this paper is to evaluate two different processes for paracetamol removal. The catalytic wet air oxidation (CWAO) of paracetamol on activated carbon was investigated both as a water treatment technique using an autoclave reactor and as a regenerative treatment of the carbon after adsorption in a sequential fixed bed process. Three activated carbons (ACs) from different source materials were used as catalysts: two microporous basic ACs (S23 and C1) and a meso- and micro-porous acidic one (L27). During the first CWAO experiment the adsorption capacity and catalytic performance of fresh S23 and C1 were higher than those of fresh L27 despite its higher surface area. This situation changed after AC reuse, as finally L27 gave the best results after five CWAO cycles. Respirometry tests with activated sludge revealed that in the studied conditions the use of CWAO enhanced the aerobic biodegradability of the effluent. In the ADOX process L27 also showed better oxidation performances and regeneration efficiency. This different ageing was examined through AC physico-chemical properties.

Non-thermal plasmas for non-catalytic and catalytic VOC abatement

International Nuclear Information System (INIS)

Vandenbroucke, Arne M.; Morent, Rino; De Geyter, Nathalie; Leys, Christophe

2011-01-01

Highlights: → We review the current status of catalytic and non-catalytic VOC abatement based on a vast number of research papers. → The underlying mechanisms of plasma-catalysis for VOC abatement are discussed. → Critical process parameters that determine the influent are discussed and compared. - Abstract: This paper reviews recent achievements and the current status of non-thermal plasma (NTP) technology for the abatement of volatile organic compounds (VOCs). Many reactor configurations have been developed to generate a NTP at atmospheric pressure. Therefore in this review article, the principles of generating NTPs are outlined. Further on, this paper is divided in two equally important parts: plasma-alone and plasma-catalytic systems. Combination of NTP with heterogeneous catalysis has attracted increased attention in order to overcome the weaknesses of plasma-alone systems. An overview is given of the present understanding of the mechanisms involved in plasma-catalytic processes. In both parts (plasma-alone systems and plasma-catalysis), literature on the abatement of VOCs is reviewed in close detail. Special attention is given to the influence of critical process parameters on the removal process.

Hydrophobic and hydrophilic nanosheet catalysts with high catalytic activity and recycling stability through control of the outermost ligand

Science.gov (United States)

Ko, Younji; Kim, Donghee; Kwon, Cheong Hoon; Cho, Jinhan

2018-04-01

In this study, we introduce hydrophobic and hydrophilic graphene oxide nanosheet (GON) catalysts prepared by consecutive ligand replacement of hydrophobically stabilized magnetic and catalytic nanoparticles (NPs); it exhibits high catalytic activity, fast magnetic response, and good dispersion in both nonpolar and aqueous media, allowing high loading amount of magnetic and catalytic NPs onto GON sheets. More specifically, these GON catalysts showed a high product yield of 66-99% and notable recyclability (93% of the initial product yield after 10 reaction cycles) in a Suzuki-Miyaura reaction in nonpolar media, outperforming the performance of the conventional hydrophilic GON catalysts. Additional coating of a hydrophilic layer onto GON catalysts also showed the notable performance (product yield ∼99%) in catalytic reactions performed in aqueous media. Given that ligand-controlled catalytic NPs adsorbed onto 2D nanosheets can be used as hydrophobic and hydrophilic stabilizers as well as catalysts, our approach can provide a tool for developing and designing 2D-nanosheet catalysts with high performance in nonpolar and polar media.

Catalytic distillation process

Science.gov (United States)

Smith, L.A. Jr.

1982-06-22

A method is described for conducting chemical reactions and fractionation of the reaction mixture comprising feeding reactants to a distillation column reactor into a feed zone and concurrently contacting the reactants with a fixed bed catalytic packing to concurrently carry out the reaction and fractionate the reaction mixture. For example, a method for preparing methyl tertiary butyl ether in high purity from a mixed feed stream of isobutene and normal butene comprising feeding the mixed feed stream to a distillation column reactor into a feed zone at the lower end of a distillation reaction zone, and methanol into the upper end of said distillation reaction zone, which is packed with a properly supported cationic ion exchange resin, contacting the C[sub 4] feed and methanol with the catalytic distillation packing to react methanol and isobutene, and concurrently fractionating the ether from the column below the catalytic zone and removing normal butene overhead above the catalytic zone.

Catalytic oxidation of soot over alkaline niobates

International Nuclear Information System (INIS)

Pecchi, G.; Cabrera, B.; Buljan, A.; Delgado, E.J.; Gordon, A.L.; Jimenez, R.

2013-01-01

Highlights: ► No previous reported studies about alkaline niobates as catalysts for soot oxidation. ► NaNbO 3 and KNbO 3 perovskite-type oxides show lower activation energy than other lanthanoid perovskite-type oxides. ► The alkaline niobate does not show deactivation by metal loss. - Abstract: The lack of studies in the current literature about the assessment of alkaline niobates as catalysts for soot oxidation has motivated this research. In this study, the synthesis, characterization and assessment of alkaline metal niobates as catalysts for soot combustion are reported. The solids MNbO 3 (M = Li, Na, K, Rb) are synthesized by a citrate method, calcined at 450 °C, 550 °C, 650 °C, 750 °C, and characterized by AAS, N 2 adsorption, XRD, O 2 -TPD, FTIR and SEM. All the alkaline niobates show catalytic activity for soot combustion, and the activity depends basically on the nature of the alkaline metal and the calcination temperature. The highest catalytic activity, expressed as the temperature at which combustion of carbon black occurs at the maximum rate, is shown by KNbO 3 calcined at 650 °C. At this calcination temperature, the catalytic activity follows an order dependent on the atomic number, namely: KNbO 3 > NaNbO 3 > LiNbO 3 . The RbNbO 3 solid do not follow this trend presumably due to the perovskite structure was not reached. The highest catalytic activity shown by of KNbO 3 , despite the lower apparent activation energy of NaNbO 3 , stress the importance of the metal nature and suggests the hypothesis that K + ions are the active sites for soot combustion. It must be pointed out that alkaline niobate subjected to consecutive soot combustion cycles does not show deactivation by metal loss, due to the stabilization of the alkaline metal inside the perovskite structure.

Degradation of paracetamol by catalytic wet air oxidation and sequential adsorption - Catalytic wet air oxidation on activated carbons

Energy Technology Data Exchange (ETDEWEB)

Quesada-Penate, I. [Universite de Toulouse, INPT, UPS, Laboratoire de Genie Chimique, 4, Allee Emile Monso, F-31432 Toulouse (France); CNRS, Laboratoire de Genie Chimique, F-31432 Toulouse (France); Julcour-Lebigue, C., E-mail: carine.julcour@ensiacet.fr [Universite de Toulouse, INPT, UPS, Laboratoire de Genie Chimique, 4, Allee Emile Monso, F-31432 Toulouse (France); CNRS, Laboratoire de Genie Chimique, F-31432 Toulouse (France); Jauregui-Haza, U. J. [Instituto Superior de Tecnologias y Ciencias Aplicadas, Ave. Salvador Allende y Luaces, Habana (Cuba); Wilhelm, A. M.; Delmas, H. [Universite de Toulouse, INPT, UPS, Laboratoire de Genie Chimique, 4, Allee Emile Monso, F-31432 Toulouse (France); CNRS, Laboratoire de Genie Chimique, F-31432 Toulouse (France)

2012-06-30

Highlights: Black-Right-Pointing-Pointer Three activated carbons (AC) compared as adsorbents and oxidation catalysts. Black-Right-Pointing-Pointer Similar evolution for catalytic and adsorptive properties of AC over reuses. Black-Right-Pointing-Pointer Acidic and mesoporous AC to be preferred, despite lower initial efficiency. Black-Right-Pointing-Pointer Oxidative degradation of paracetamol improves biodegradability. Black-Right-Pointing-Pointer Convenient hybrid adsorption-regenerative oxidation process for continuous treatment. - Abstract: The concern about the fate of pharmaceutical products has raised owing to the increasing contamination of rivers, lakes and groundwater. The aim of this paper is to evaluate two different processes for paracetamol removal. The catalytic wet air oxidation (CWAO) of paracetamol on activated carbon was investigated both as a water treatment technique using an autoclave reactor and as a regenerative treatment of the carbon after adsorption in a sequential fixed bed process. Three activated carbons (ACs) from different source materials were used as catalysts: two microporous basic ACs (S23 and C1) and a meso- and micro-porous acidic one (L27). During the first CWAO experiment the adsorption capacity and catalytic performance of fresh S23 and C1 were higher than those of fresh L27 despite its higher surface area. This situation changed after AC reuse, as finally L27 gave the best results after five CWAO cycles. Respirometry tests with activated sludge revealed that in the studied conditions the use of CWAO enhanced the aerobic biodegradability of the effluent. In the ADOX process L27 also showed better oxidation performances and regeneration efficiency. This different ageing was examined through AC physico-chemical properties.

Efficient catalytic system for the direct transformation of lignocellulosic biomass to furfural and 5-hydroxymethylfurfural.

Science.gov (United States)

Zhang, Luxin; Xi, Guoyun; Zhang, Jiaxin; Yu, Hongbing; Wang, Xiaochang

2017-01-01

A feasible approach was developed for the co-production of 5-hydroxymethylfurfural (5-HMF) and furfural from corncob via a new porous polytriphenylamine-SO 3 H (SPTPA) solid acid catalyst in lactone solvents. XRD, SEM, XPS, N 2 adsorption-desorption, elemental analysis, TG-DTA, acid-base titration and FTIR spectroscopy techniques were used to characterize the catalyst. This study demonstrates and optimizes the catalytic performance of SPTPA and solvent selection. SPTPA was found to exhibit superior catalytic ability in γ-valerolactone (GVL). Under the optimum reaction conditions, simultaneously encouraging yields of furfural (73.9%) and 5-HMF (32.3%) were achieved at 448K. The main advantages of this process include reasonable yields of both 5-HMF and furfural in the same reaction system, practical simplicity for the raw biomass utilization, and the use of a safe and environmentally benign solvent. Copyright © 2016 Elsevier Ltd. All rights reserved.

Ammonium generation during SRAT cycle

International Nuclear Information System (INIS)

Hsu, C.W.

1992-01-01

During the IDMS noble-metal demonstration runs ammonium nitrate deposition was found in the vessel vent system of the feed preparation area. In the bench-scale experiments of studying the hydrogen generation during the sludge treatment cycle, ammonium ion production was also monitored. It was found that: During a simulation of the DWPF Cold Chemical Runs SRAT cycle no detectable amount of ammonium ions was generated when treating a non-noble-metal containing sludge simulant according to the nitric acid flowsheet. Ammonium ions were generated during the SRAT-SME cycle when treating the noble-metal containing sludge with either formic acid or nitric acid/late-washing PHA. This is due to the reaction between formic acid and nitrate catalyzed by the noble metals in the sludge simulant. Ammonium ion production closely followed the hydrogen evolution from the catalytic decomposition of formic acid. This report summarizes the results of the production of ammonia during the SRAT cycle

Catalytic bioreactors and methods of using same

Science.gov (United States)

Worden, Robert Mark; Liu, Yangmu Chloe

2017-07-25

Various embodiments provide a bioreactor for producing a bioproduct comprising one or more catalytically active zones located in a housing and adapted to keep two incompatible gaseous reactants separated when in a gas phase, wherein each of the one or more catalytically active zones may comprise a catalytic component retainer and a catalytic component retained within and/or thereon. Each of the catalytically active zones may additionally or alternatively comprise a liquid medium located on either side of the catalytic component retainer. Catalytic component may include a microbial cell culture located within and/or on the catalytic component retainer, a suspended catalytic component suspended in the liquid medium, or a combination thereof. Methods of using various embodiments of the bioreactor to produce a bioproduct, such as isobutanol, are also provided.

Degradation of paracetamol by catalytic wet air oxidation and sequential adsorption - Catalytic wet air oxidation on activated carbons.

Science.gov (United States)

Quesada-Peñate, I; Julcour-Lebigue, C; Jáuregui-Haza, U J; Wilhelm, A M; Delmas, H

2012-06-30

The concern about the fate of pharmaceutical products has raised owing to the increasing contamination of rivers, lakes and groundwater. The aim of this paper is to evaluate two different processes for paracetamol removal. The catalytic wet air oxidation (CWAO) of paracetamol on activated carbon was investigated both as a water treatment technique using an autoclave reactor and as a regenerative treatment of the carbon after adsorption in a sequential fixed bed process. Three activated carbons (ACs) from different source materials were used as catalysts: two microporous basic ACs (S23 and C1) and a meso- and micro-porous acidic one (L27). During the first CWAO experiment the adsorption capacity and catalytic performance of fresh S23 and C1 were higher than those of fresh L27 despite its higher surface area. This situation changed after AC reuse, as finally L27 gave the best results after five CWAO cycles. Respirometry tests with activated sludge revealed that in the studied conditions the use of CWAO enhanced the aerobic biodegradability of the effluent. In the ADOX process L27 also showed better oxidation performances and regeneration efficiency. This different ageing was examined through AC physico-chemical properties. Copyright © 2012 Elsevier B.V. All rights reserved.

Catalytic Palladium Film Deposited by Scalable Low-Temperature Aqueous Combustion.

Science.gov (United States)

Voskanyan, Albert A; Li, Chi-Ying Vanessa; Chan, Kwong-Yu

2017-09-27

This article describes a novel method for depositing a dense, high quality palladium thin film via a one-step aqueous combustion process which can be easily scaled up. Film deposition of Pd from aqueous solutions by conventional chemical or electrochemical methods is inhibited by hydrogen embrittlement, thus resulting in a brittle palladium film. The method outlined in this work allows a direct aqueous solution deposition of a mirror-bright, durable Pd film on substrates including glass and glassy carbon. This simple procedure has many advantages including a very high deposition rate (>10 cm 2 min -1 ) and a relatively low deposition temperature (250 °C), which makes it suitable for large-scale industrial applications. Although preparation of various high-quality oxide films has been successfully accomplished via solution combustion synthesis (SCS) before, this article presents the first report on direct SCS production of a metallic film. The mechanism of Pd film formation is discussed with the identification of a complex formed between palladium nitrate and glycine at low temperature. The catalytic properties and stability of films are successfully tested in alcohol electrooxidation and electrochemical oxygen reduction reaction. It was observed that combustion deposited Pd film on a glassy carbon electrode showed excellent catalytic activity in ethanol oxidation without using any binder or additive. We also report for the first time the concept of a reusable "catalytic flask" as illustrated by the Suzuki-Miyaura cross-coupling reaction. The Pd film uniformly covers the inner walls of the flask and eliminates the catalyst separation step. We believe the innovative concept of a reusable catalytic flask is very promising and has the required features to become a commercial product in the future.

TEMPO functionalized C60 fullerene deposited on gold surface for catalytic oxidation of selected alcohols

International Nuclear Information System (INIS)

Piotrowski, Piotr; Pawłowska, Joanna; Sadło, Jarosław Grzegorz; Bilewicz, Renata; Kaim, Andrzej

2017-01-01

C 60 TEMPO 10 catalytic system linked to a microspherical gold support through a covalent S-Au bond was developed. The C 60 TEMPO 10 @Au composite catalyst had a particle size of 0.5–0.8 μm and was covered with the fullerenes derivative of 2.3 nm diameter bearing ten nitroxyl groups; the organic film showed up to 50 nm thickness. The catalytic composite allowed for the oxidation under mild conditions of various primary and secondary alcohols to the corresponding aldehyde and ketone analogues with efficiencies as high as 79–98%, thus giving values typical for homogeneous catalysis, while retaining at the same time all the advantages of heterogeneous catalysis, e.g., easy separation by filtration from the reaction mixture. The catalytic activity of the resulting system was studied by means of high pressure liquid chromatography. A redox mechanism was proposed for the process. In the catalytic cycle of the oxidation process, the TEMPO moiety was continuously regenerated in situ with an applied primary oxidant, for example, O 2 /Fe 3+ system. The new intermediate composite components and the final catalyst were characterized by various spectroscopic methods and thermogravimetry.

Production of filamentous carbon and H{sub 2} by solarthermal catalytic cracking of CH{sub 4}

Energy Technology Data Exchange (ETDEWEB)

Kirillov, V; Kuvshinov, G [Boreskov Inst. of Catalysis (Russian Federation); Reller, A [Hamburg Univ., Hamburg (Germany); Steinfeld, A [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

1997-06-01

The catalytic thermal decomposition of methane has been experimentally studied using high-temperature solar process heat. Nickel catalyst particles, fluidized in methane, were directly irradiated at the PSI solar furnace. Carbon deposition consisted of randomly interlaced filaments that grew as fibers and hollow nanotubes (of approx. 30 nm diameter) originating at each catalytic particle. (author) 4 figs., 7 refs.

Development and test of a new catalytic converter for natural gas ...

Indian Academy of Sciences (India)

catalytic converter and a new natural gas engine such as compressed natural gas. (CNG) direct ..... bility to store oxygen from random gas flow within the substrate in comparison to flow through ..... and behaviour in the water–gas shift reaction.

Organic Rankine cycle – review and research directions in engine applications

Directory of Open Access Journals (Sweden)

Panesar Angad

2017-01-01

Full Text Available Waste heat to power conversion using Organic Rankine Cycles (ORC is expected to play an important role in CO2 reductions from diesel engines. Firstly, a review of automotive ORCs is presented focusing on the pure working fluids, thermal architectures and expanders. The discussion includes, but is not limited to: R245fa, ethanol and water as fluids; series, parallel and cascade as architectures; dry saturated, superheated and supercritical as expansion conditions; and scroll, radial turbine and piston as expansion machines. Secondly, research direction in versatile expander and holistic architecture (NOx + CO2 are proposed. Benefits of using the proposed unconventional approaches are quantified using Ricardo Wave and Aspen HYSYS for diesel engine and ORC modelling. Results indicate that, the implementation of versatile piston expander tolerant to two-phase and using cyclopentane can potentially increase the highway drive cycle power by 8%. Furthermore, holistic architecture offering complete utilisation of charge air and exhaust recirculation heat increased the performance noticeably to 5% of engine power at the design point condition.

Catalysis looks to the future. Panel on new directions in catalytic science and technology

Energy Technology Data Exchange (ETDEWEB)

1992-12-31

Catalysts play a vital role in providing society with fuels, commodity and fine chemicals, pharmaceuticals, and means for protecting the environment. To be useful, a good catalyst must have a high turnover frequency (activity), produce the right kind of product (selectivity), and have a long life (durability), all at an acceptable cost. Research in the field of catalysis provides the tools and understanding required to facilitate and accelerate the development of improved catalysts and to open opportunities for the discovery of new catalytic processes. The aim of this report is to identify the research opportunities and challenges for catalysis in the coming decades and to detail the resources necessary to ensure steady progress. Chapter 2 discusses opportunities for developing new catalysts to meet the demands of the chemical and fuel industries, and the increasing role of catalysis in environmental protection. The intellectual challenges for advancing the frontiers of catalytic science are outlined in Chapter 3. The human and institutional resources available in the US for carrying out research on catalysis are summarized in Chapter 4. The findings and recommendations of the panel for industry, academe, the national laboratories, and the federal government are presented in Chapter 5.

Catalytic process for tritium exchange reaction

International Nuclear Information System (INIS)

Hansoo Lee; Kang, H.S.; Paek, S.W.; Hongsuk Chung; Yang Geun Chung; Sook Kyung Lee

2001-01-01

The catalytic activities for a hydrogen isotope exchange were measured through the reaction of a vapor and gas mixture. The catalytic activity showed to be comparable with the published data. Since the gas velocity is relatively low, the deactivation was not found clearly during the 5-hour experiment. Hydrogen isotope transfer experiments were also conducted through the liquid phase catalytic exchange reaction column that consisted of a catalytic bed and a hydrophilic bed. The efficiencies of both the catalytic and hydrophilic beds were higher than 0.9, implying that the column performance was excellent. (author)

In-situ reduced silver nanoparticles on populus fiber and the catalytic application

Energy Technology Data Exchange (ETDEWEB)

Li, Miaomiao; Gong, Yumei, E-mail: ymgong@dlpu.edu.cn; Wang, Wenheng; Xu, Guangpeng; Liu, Yuanfa; Guo, Jing, E-mail: guojing8161@163.com

2017-02-01

Highlights: • A composite involved in in-situ chelating AgNPs on natural cellulose was prepared. • Polyamidoxime grafted from the cellulose adsorbed Ag+ which was reduced to AgNPs. • The composite exhibits excellent catalytic activity in reducing 4-nitrophenol. - Abstract: One kind of composites involved in silver nanoparticles (AgNPs) loading in-situ on natural populus fiber (PF) matrix was prepared by polyamidoxime (PAO) functionalized the cellulose fiber. In which PAO worked as trapping and stabilizing agents chelating silver ions and made it reduced in-situ to obtain AgNPs by borohydride at room temperature. The synthesized composites were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). Moreover, the composites showed significant catalytic activity 1.87 s{sup −1} g{sup −1} and repeated usability more than 7 cycles in reducing 4-nitrophenol (4-NP) into 4-aminophenol (4-AP) detected by UV–vis spectrophotometer in aqueous solution due to the surface-enhanced immobility and large amount of AgNPs. The natural cellulose fiber provides a green platform to react and support other noble metals for wide catalytic reactions.

Solid strong base K-Pt/NaY zeolite nano-catalytic system for completed elimination of formaldehyde at room temperature

Science.gov (United States)

Song, Shaoqing; Wu, Xi; Lu, Changhai; Wen, Meicheng; Le, Zhanggao; Jiang, Shujuan

2018-06-01

Solid strong base nano-catalytic system of K-modification NaY zeolite supported 0.08% Pt (K-Pt/NaY) were constructed for eliminating HCHO at room temperature. In the catalytic process, activation energy over K-Pt/NaY nano-catalytic system was greatly decreased along with the enhanced reaction rate. Characterization and catalytic tests revealed the surface electron structure of K-Pt/NaY was improved, as reflected by the enhanced HCHO adsorption capability, high sbnd OH concentration, and low-temperature reducibility. Therefore, the optimal K-Pt/NaY showed high catalytic efficiency and strong H2O tolerance for HCHO elimination by directly promoting the reaction between active sbnd OH and formate species. These results may suggest a new way for probing the advanced solid strong base nano-catalytic system for the catalytic elimination of indoor HCHO.

The Direct Internal Recycling concept to simplify the fuel cycle of a fusion power plant

International Nuclear Information System (INIS)

Day, Christian; Giegerich, Thomas

2013-01-01

Highlights: • The fusion fuel cycle is presented and its functions are discussed. • Tritium inventories are estimated for an early DEMO configuration. • The Direct Internal Recycling concept to reduce tritium inventories is described. • Concepts for its technical implementation are developed. -- Abstract: A new concept, the Direct Internal Recycling (DIR) concept, is proposed, which minimizes fuel cycle inventory by adding an additional short-cut between the pumped torus exhaust gas and the fuelling systems. The paper highlights quantitative modelling results derived from a simple fuel cycle spreadsheet which underline the potential benefits that can be achieved by implementation of the DIR concept into a fusion power plant. DIR requires a novel set-up of the torus exhaust pumping system, which replaces the batch-wise and cyclic operated cryogenic pumps by a continuous pumping solution and which offers at the same time an additional integral gas separation function. By that, hydrogen can be removed close to the divertor from all other gases and the main load to the fuel clean-up systems is a smaller, helium-rich gas stream. Candidate DIR relevant pump technology based on liquid metals (vapour diffusion and liquid ring pumps) and metal foils is discussed

Effects of catalytic hydrotreating on light cycle oil fuel quality

International Nuclear Information System (INIS)

Anabtawi, J.A.; Ali, S.A.

1991-01-01

This paper reports on a pilot plant study that was conducted to evaluate three commercial catalysts for hydrotreating of light cycle oil to reduce its aromatic content and improve the cetane index. The operating parameters were varied between 325 and 400 degrees C, 1 and 3 h - 1 , and 4 and 10 MPa at 535 L/L. The data showed that, in general, the product density and aromatic content decreased as the temperature or pressure increased or space velocity decreased. The cetane index improvement ranged from 7.3 to 10.0 for the Ni-W/Al 2 O 3 catalyst and from 6.1 to 10.1 for the Ni-Mo/Al 2 O 3 catalysts. The catalyst performance was evaluated in terms of hydrodesulfurization, hydrodenitrogenation, hydrogenation, aromatic saturation, and hydrogen consumption. This study confirms that light cycle oil can be hydrotreated to improve its cetane quality, thus increasing the extent of its blending ratio into the diesel pool

Fe-Mn bi-metallic oxides loaded on granular activated carbon to enhance dye removal by catalytic ozonation.

Science.gov (United States)

Tang, Shoufeng; Yuan, Deling; Zhang, Qi; Liu, Yameng; Zhang, Qi; Liu, Zhengquan; Huang, Haiming

2016-09-01

A Fe-Mn bi-metallic oxide supported on granular activated carbon (Fe-Mn GAC) has been fabricated by an impregnation-desiccation method and tested in the catalytic ozonation of methyl orange (MO) degradation and mineralization. X-ray diffraction, scanning electron microscopy, and Fourier transform infrared spectroscopy characterizations revealed that Fe-Mn oxides were successfully loaded and uniformly distributed on the GAC, and nitrogen adsorption isotherms showed that the supported GAC retained a large surface area and a high pore volume compared with the pristine GAC. The catalytic activity was systematically assessed by monitoring the MO removal efficiencies at different operational parameters, such as catalyst dosage, initial solution pH, and ozone flow rate. The Fe-Mn GAC exhibited better catalytic activity relative to ozone alone and GAC alone, improving the TOC removal by 24.5 and 11.5 % and COD removal by 13.6 and 7.3 %, respectively. The reusability of the hybrid was examined over five consecutive cyclic treatments. The Fe-Mn GAC catalytic activity was only a slight loss in the cycles, showing good stability. The addition of Na2CO3 as hydroxyl radicals (•OH) scavengers proved that the catalytic ozonation mechanism was the enhanced generation of •OH by the Fe-Mn GAC. The above results render the Fe-Mn GAC an industrially promising candidate for catalytic ozonation of dye contaminant removal.

Effect of High-Pressure Treatment on Catalytic and Physicochemical Properties of Pepsin.

Science.gov (United States)

Wang, Jianan; Bai, Tenghui; Ma, Yaping; Ma, Hanjun

2017-10-11

For a long time, high-pressure treatment has been used to destroy the compact structures of natural proteins in order to promote subsequent enzymatic hydrolysis. However, there are few reports evaluating the feasibility of directly improving the catalytic capability of proteases by using high-pressure treatments. In this study, the effects of high-pressure treatment on the catalytic capacity and structure of pepsin were investigated, and the relationship between its catalytic properties and changes in its physicochemical properties was explored. It was found that high-pressure treatment could lead to changes of the sulfhydryl group/disulfide bond content, hydrophobicity, hydrodynamic radius, intrinsic viscosity, and subunit composition of pepsin, and the conformational change of pepsin resulted in improvement to its enzymatic activity and hydrolysis efficiency, which had an obvious relationship with the high-pressure treatment conditions.

Life cycle assessment of selective non-catalytic reduction (SNCR) of nitrous oxides in a full-scale municipal solid waste incinerator

DEFF Research Database (Denmark)

Møller, Jacob; Munk, Bjarne; Crillesen, Kim

2011-01-01

Selective non-catalytic reduction (SNCR) of nitrous oxides in a full-scale municipal solid waste incinerator was investigated using LCA. The relationship between NOx-cleaning and ammonia dosage was measured at the plant. Un-reacted ammonia – the ammonia slip – leaving the flue-gas cleaning system......-cleaning efficiency, the fate of the ammonia slip as well as the environmental impact from ammonia production, the potential acidification and nutrient enrichment from NOx-cleaning was calculated as a function of ammonia dosage. Since the exact fate of the ammonia slip could not be measured directly, a number...... of scenarios were set up ranging from “best case” with no ammonia from the slip ending up in the environment to “worst case” where all the ammonia slip eventually ended up in the environment and contributed to environmental pollution. In the “best case” scenario the highest ammonia dosage was most beneficial...

Contributions to the theory of catalytic titrations-III Neutralization catalytic titrations.

Science.gov (United States)

Gaál, F F; Abramović, B F

1985-07-01

Neutralization catalytic titrations of weak monoprotic adds and bases with both volumetric and coulometric addition of the titrant (strong base/acid) have been simulated by taking into account the equilibrium concentration of the catalyst during the titration. The influence of several factors on the shape of the simulated catalytic titration curve has been investigated and is discussed.

Catalytic conversion of light alkanes

Energy Technology Data Exchange (ETDEWEB)

Lyons, J.E.

1992-06-30

The second Quarterly Report of 1992 on the Catalytic Conversion of Light Alkanes reviews the work done between April 1, 1992 and June 31, 1992 on the Cooperative Agreement. The mission of this work is to devise a new catalyst which can be used in a simple economic process to convert the light alkanes in natural gas to oxygenate products that can either be used as clean-burning, high octane liquid fuels, as fuel components or as precursors to liquid hydrocarbon uwspomdon fuel. During the past quarter we have continued to design, prepare, characterize and test novel catalysts for the mild selective reaction of light hydrocarbons with air or oxygen to produce alcohols directly. These catalysts are designed to form active metal oxo (MO) species and to be uniquely active for the homolytic cleavage of the carbon-hydrogen bonds in light alkanes producing intermediates which can form alcohols. We continue to investigate three molecular environments for the active catalytic species that we are trying to generate: electron-deficient macrocycles (PHASE I), polyoxometallates (PHASE II), and regular oxidic lattices including zeolites and related structures as well as other molecular surface structures having metal oxo groups (PHASE I).

Synthesis and utilization of catalytically cracked cashew nut shell liquid in a diesel engine

KAUST Repository

Vedharaj, S.; Vallinayagam, R.; Yang, W.M.; Saravanan, C.G.; Roberts, William L.

2015-01-01

In this study, CNSL (Cashew nut shell liquid), an economically viable feedstock among the other contemporary resources, has been considered as an appropriate source of alternate fuel. Herein, CNSL was extracted from cashew nut outer shell, a waste product, through a unique approach of steam treatment process followed by mechanical crushing technique. In contrast to the past studies that have attempted to use unprocessed CNSL directly as substitute for diesel, this study has resorted to use processed CNSL by cracking it using zeolite catalyst. Thus, both the extraction of CNSL from cashew nut outer shell and processing of it through catalytic cracking process to help synthesize CC-CNSL (catalytically cracked CNSL) are different, which underscores the significance of the current work. In wake of adopting such distinct methodologies with fuel characterization, the properties of CC-CNSL such as viscosity and calorific value were figured out to be improved. Subsequently, CC-CNSL20 (20% CC-CNSL and 80% diesel) was tested at different fuel injection pressure such as 200 bar, 235 bar, 270 bar and 300 bar so as to optimize its use in a single cylinder diesel engine. From the engine experimental study, CC-CNSL20 was found to evince better engine performance than diesel and the composite emissions of CO (carbon monoxide), HC (hydrocarbon), NOX (oxides of nitrogen) and smoke, computed based on ISO 8178 D2 standard test cycle, were found to be better than diesel and incompliance with the legislative norms for genset.

Synthesis and utilization of catalytically cracked cashew nut shell liquid in a diesel engine

KAUST Repository

Vedharaj, S.

2015-09-30

In this study, CNSL (Cashew nut shell liquid), an economically viable feedstock among the other contemporary resources, has been considered as an appropriate source of alternate fuel. Herein, CNSL was extracted from cashew nut outer shell, a waste product, through a unique approach of steam treatment process followed by mechanical crushing technique. In contrast to the past studies that have attempted to use unprocessed CNSL directly as substitute for diesel, this study has resorted to use processed CNSL by cracking it using zeolite catalyst. Thus, both the extraction of CNSL from cashew nut outer shell and processing of it through catalytic cracking process to help synthesize CC-CNSL (catalytically cracked CNSL) are different, which underscores the significance of the current work. In wake of adopting such distinct methodologies with fuel characterization, the properties of CC-CNSL such as viscosity and calorific value were figured out to be improved. Subsequently, CC-CNSL20 (20% CC-CNSL and 80% diesel) was tested at different fuel injection pressure such as 200 bar, 235 bar, 270 bar and 300 bar so as to optimize its use in a single cylinder diesel engine. From the engine experimental study, CC-CNSL20 was found to evince better engine performance than diesel and the composite emissions of CO (carbon monoxide), HC (hydrocarbon), NOX (oxides of nitrogen) and smoke, computed based on ISO 8178 D2 standard test cycle, were found to be better than diesel and incompliance with the legislative norms for genset.

Switch in Site of Inhibition: A Strategy for Structure-Based Discovery of Human Topoisomerase IIα Catalytic Inhibitors

Science.gov (United States)

2015-01-01

A study of structure-based modulation of known ligands of hTopoIIα, an important enzyme involved in DNA processes, coupled with synthesis and in vitro assays led to the establishment of a strategy of rational switch in mode of inhibition of the enzyme’s catalytic cycle. 6-Arylated derivatives of known imidazopyridine ligands were found to be selective inhibitors of hTopoIIα, while not showing TopoI inhibition and DNA binding. Interestingly, while the parent imidazopyridines acted as ATP-competitive inhibitors, arylated derivatives inhibited DNA cleavage similar to merbarone, indicating a switch in mode of inhibition from ATP-hydrolysis to the DNA-cleavage stage of catalytic cycle of the enzyme. The 6-aryl-imidazopyridines were relatively more cytotoxic than etoposide in cancer cells and less toxic to normal cells. Such unprecedented strategy will encourage research on “choice-based change” in target-specific mode of action for rapid drug discovery. PMID:25941559

Catalytic strategy used by the myosin motor to hydrolyze ATP.

Science.gov (United States)

Kiani, Farooq Ahmad; Fischer, Stefan

2014-07-22

Myosin is a molecular motor responsible for biological motions such as muscle contraction and intracellular cargo transport, for which it hydrolyzes adenosine 5'-triphosphate (ATP). Early steps of the mechanism by which myosin catalyzes ATP hydrolysis have been investigated, but still missing are the structure of the final ADP·inorganic phosphate (Pi) product and the complete pathway leading to it. Here, a comprehensive description of the catalytic strategy of myosin is formulated, based on combined quantum-classical molecular mechanics calculations. A full exploration of catalytic pathways was performed and a final product structure was found that is consistent with all experiments. Molecular movies of the relevant pathways show the different reorganizations of the H-bond network that lead to the final product, whose γ-phosphate is not in the previously reported HPγO4(2-) state, but in the H2PγO4(-) state. The simulations reveal that the catalytic strategy of myosin employs a three-pronged tactic: (i) Stabilization of the γ-phosphate of ATP in a dissociated metaphosphate (PγO3(-)) state. (ii) Polarization of the attacking water molecule, to abstract a proton from that water. (iii) Formation of multiple proton wires in the active site, for efficient transfer of the abstracted proton to various product precursors. The specific role played in this strategy by each of the three loops enclosing ATP is identified unambiguously. It explains how the precise timing of the ATPase activation during the force generating cycle is achieved in myosin. The catalytic strategy described here for myosin is likely to be very similar in most nucleotide hydrolyzing enzymes.

A QM/MM study of the catalytic mechanism of nicotinamidase.

Science.gov (United States)

Sheng, Xiang; Liu, Yongjun

2014-02-28

Nicotinamidase (Pnc1) is a member of Zn-dependent amidohydrolases that hydrolyzes nicotinamide (NAM) to nicotinic acid (NA), which is a key step in the salvage pathway of NAD(+) biosynthesis. In this paper, the catalytic mechanism of Pnc1 has been investigated by using a combined quantum-mechanical/molecular-mechanical (QM/MM) approach based on the recently obtained crystal structure of Pnc1. The reaction pathway, the detail of each elementary step, the energetics of the whole catalytic cycle, and the roles of key residues and Zn-binding site are illuminated. Our calculation results indicate that the catalytic water molecule comes from the bulk solvent, which is then deprotonated by residue D8. D8 functions as a proton transfer station between C167 and NAM, while the activated C167 serves as the nucleophile. The residue K122 only plays a role in stabilizing intermediates and transition states. The oxyanion hole formed by the amide backbone nitrogen atoms of A163 and C167 has the function to stabilize the hydroxyl anion of nicotinamide. The Zn-binding site rather than a single Zn(2+) ion acts as a Lewis acid to influence the reaction. Two elementary steps, the activation of C167 in the deamination process and the decomposition of catalytic water in the hydrolysis process, correspond to the large energy barriers of 25.7 and 28.1 kcal mol(-1), respectively, meaning that both of them contribute a lot to the overall reaction barrier. Our results may provide useful information for the design of novel and efficient Pnc1 inhibitors and related biocatalytic applications.

Self-catalytic stabilized Ag-Cu nanoparticles with tailored SERS response for plasmonic photocatalysis

Science.gov (United States)

He, Lili; Liu, Changqing; Tang, Jia; Zhou, Youchen; Yang, Hui; Liu, Ruiyu; Hu, Jiugang

2018-03-01

In-situ SERS monitoring of direct plasmon-driven photocatalysis was achieved using relatively earth-abundant Cu NPs following their decoration with tiny amounts of silver, which promoted excellent SERS and high catalytic activity. The SERS and catalytic performance of the Ag-Cu NPs can be tuned by changing their composition. In particular, it was found that the surface oxidation state of copper could be switched to its metallic state via self-plasmon catalysis under laser irradiation, highlighting the potential of air-unstable copper NPs as stable plasmonic catalysts. These dual functional Ag-Cu NPs were used for SERS real-time monitoring of plasmon-driven photocatalysis reactions involving the degradation of Rhodamine 6G and the dimerization of 4-nitrothiophenol. The corresponding catalytic reaction mechanisms were discussed.

Outstanding catalytic activity of ultra-pure platinum nanoparticles.

Science.gov (United States)

Januszewska, Aneta; Dercz, Grzegorz; Piwowar, Justyna; Jurczakowski, Rafal; Lewera, Adam

2013-12-09

Small (4 nm) nanoparticles with a narrow size distribution, exceptional surface purity, and increased surface order, which exhibits itself as an increased presence of basal crystallographic planes, can be obtained without the use of any surfactant. These nanoparticles can be used in many applications in an as-received state and are threefold more active towards a model catalytic reaction (oxidation of ethylene glycol). Furthermore, the superior properties of this material are interesting not only due to the increase in their intrinsic catalytic activity, but also due to the exceptional surface purity itself. The nanoparticles can be used directly (i.e., as-received, without any cleaning steps) in biomedical applications (i.e., as more efficient drug carriers due to an increased number of adsorption sites) and in energy-harvesting/data-storage devices. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface Reduced CeO2 Nanowires for Direct Conversion of CO2 and Methanol to Dimethyl Carbonate: Catalytic Performance and Role of Oxygen Vacancy

Directory of Open Access Journals (Sweden)

Zhongwei Fu

2018-04-01

Full Text Available Ultralong 1D CeO2 nanowires were synthesized via an advanced solvothermal method, surface reduced under H2 atmosphere, and first applied in direct synthesis of dimethyl carbonate (DMC from CO2 and CH3OH. The micro morphologies, physical parameters of nanowires were fully investigated by transmission electron microscopy (TEM, X-ray diffraction (XRD, N2 adsorption, X-ray photoelectron spectrum (XPS, and temperature-programmed desorption of ammonia/carbon dioxide (NH3-TPD/CO2-TPD. The effects of surface oxygen vacancy and acidic/alkaline sites on the catalytic activity was explored. After reduction, the acidic/alkaline sites of CeO2 nanowires can be dramatically improved and evidently raised the catalytic performance. CeO2 nanowires reduced at 500 °C (CeO2_NW_500 exhibited notably superior activity with DMC yield of 16.85 mmol gcat−1. Furthermore, kinetic insights of initial rate were carried out and the apparent activation energy barrier of CeO2_NW_500 catalyst was found to be 41.9 kJ/mol, much tiny than that of CeO2_NW catalyst (74.7 KJ/mol.

Mechanisms of catalytic activity in heavily coated hydrocracking catalysts

Energy Technology Data Exchange (ETDEWEB)

Millan, M.; Adell, C.; Hinojosa, C.; Herod, A.A.; Kandiyoti, R. [University of London Imperial College Science Technology & Medicine, London (United Kingdom). Dept. of Chemical Engineering

2008-01-15

Catalyst deactivation by coke deposition has a direct impact on the economic viability of heavy hydrocarbon upgrading processes, such as coal liquefaction and oil residue hydroprocessing. Coke deposition is responsible for rapid loss of catalytic activity and it mostly takes place in the early stages of hydrocracking. The effect of carbonaceous deposition on the catalytic activity of a chromium pillared montmorillonite has been studied in the present work. Its catalytic activity in hydrocracking a coal extract was evaluated based on the boiling point distributions of feed and products obtained by thermogravimetric analysis (TGA), and their characterisation by size exclusion chromatography (SEC) and UV-Fluorescence spectroscopy (UV-F). A large deposition on the catalyst was observed after two successive 2-hour long runs in which the catalyst recovered from the first run was reused in the second. The pillared clay retained its activity even though it showed high carbon loading, a large drop in surface area and complete apparent pore blockage. Some observations may contribute to explain this persistent catalytic activity. First, there is evidence suggesting the dynamic nature of the carbonaceous deposits, which continuously exchange material with the liquid, allowing catalytic activity to continue. Secondly, Scanning Electron Microscopy (SEM) on the used Cr montmorillonite has shown preferential deposition on some regions of the catalyst, which leaves a fraction of the surface relatively exposed. Finally, evidence from SEM coupled to X-ray microanalysis also suggest that deposits are thinner in areas where the active phase of the catalyst is present in higher concentrations. Hydrogenation on the active sites would make the deposits more soluble in the liquid cleaning of surrounding area from deposits.

Catalytic distillation structure

Science.gov (United States)

Smith, L.A. Jr.

1984-04-17

Catalytic distillation structure is described for use in reaction distillation columns, and provides reaction sites and distillation structure consisting of a catalyst component and a resilient component intimately associated therewith. The resilient component has at least about 70 volume % open space and is present with the catalyst component in an amount such that the catalytic distillation structure consists of at least 10 volume % open space. 10 figs.

Low Temperature Selective Catalytic Reduction of Nitrogen Oxides in Production of Nitric Acid by the Use of Liquid

Directory of Open Access Journals (Sweden)

Kabljanac, Ž.

2011-11-01

Full Text Available This paper presents the application of low-temperature selective catalytic reduction of nitrous oxides in the tail gas of the dual-pressure process of nitric acid production. The process of selective catalytic reduction is carried out using the TiO2/WO3 heterogeneous catalyst applied on a ceramic honeycomb structure with a high geometric surface area per volume. The process design parameters for nitric acid production by the dual-pressure procedure in a capacity range from 75 to 100 % in comparison with designed capacity for one production line is shown in the Table 1. Shown is the effectiveness of selective catalytic reduction in the temperature range of the tail gas from 180 to 230 °C with direct application of liquid ammonia, without prior evaporation to gaseous state. The results of inlet and outlet concentrations of nitrous oxides in the tail gas of the nitric acid production process are shown in Figures 1 and 2. Figure 3 shows the temperature dependence of the selective catalytic reduction of nitrous oxides expressed as NO2in the tail gas of nitric acid production with the application of a constant mass flow of liquid ammonia of 13,0 kg h-1 and average inlet mass concentration of the nitrous oxides expressed as NO2of 800,0 mgm-3 during 100 % production capacity. The specially designed liquid-ammonia direct-dosing system along with the effective homogenization of the tail gas resulted in emission levels of nitrous oxides expressed as NO2 in tail gas ranging from 100,0 to 185,0 mg m-3. The applied low-temperature selective catalytic reduction of the nitrous oxides in the tail gases by direct use of liquid ammonia is shown in Figure 4. It is shown that low-temperature selective catalytic reduction with direct application of liquid ammonia opens a new opportunity in the reduction of nitrous oxide emissions during nitric acid production without the risk of dangerous ammonium nitrate occurring in the process of subsequent energy utilization of

Man o' War Mutation in UDP-α-D-Xylose Synthase Favors the Abortive Catalytic Cycle and Uncovers a Latent Potential for Hexamer Formation

Energy Technology Data Exchange (ETDEWEB)

Walsh, Jr., Richard M.; Polizzi, Samuel J.; Kadirvelraj, Renuka; Howard, Wesley W.; Wood, Zachary A. [Georgia

2015-03-17

The man o’ war (mow) phenotype in zebrafish is characterized by severe craniofacial defects due to a missense mutation in UDP-α-D-xylose synthase (UXS), an essential enzyme in proteoglycan biosynthesis. The mow mutation is located in the UXS dimer interface ~16 Å away from the active site, suggesting an indirect effect on the enzyme mechanism. We have examined the structural and catalytic consequences of the mow mutation (R236H) in the soluble fragment of human UXS (hUXS), which shares 93% sequence identity with the zebrafish enzyme. In solution, hUXS dimers undergo a concentration-dependent association to form a tetramer. Sedimentation velocity studies show that the R236H substitution induces the formation of a new hexameric species. Using two new crystal structures of the hexamer, we show that R236H and R236A substitutions cause a local unfolding of the active site that allows for a rotation of the dimer interface necessary to form the hexamer. The disordered active sites in the R236H and R236A mutant constructs displace Y231, the essential acid/base catalyst in the UXS reaction mechanism. The loss of Y231 favors an abortive catalytic cycle in which the reaction intermediate, UDP-α-D-4-keto-xylose, is not reduced to the final product, UDP-α-D-xylose. Surprisingly, the mow-induced hexamer is almost identical to the hexamers formed by the deeply divergent UXS homologues from Staphylococcus aureus and Helicobacter pylori (21% and 16% sequence identity, respectively). The persistence of a latent hexamer-building interface in the human enzyme suggests that the ancestral UXS may have been a hexamer.

Thermodynamic Analysis of an Integrated Solid Oxide Fuel Cell Cycle with a Rankine Cycle

DEFF Research Database (Denmark)

Rokni, Masoud

2010-01-01

Hybrid systems consisting of Solid Oxide Fuel Cells (SOFC) on the top of a Steam Turbine (ST) are investigated. The plants are fired by natural gas (NG). A desulfurization reactor removes the sulfur content in the fuel while a pre-reformer breaks down the heavier hydrocarbons. The pre-treated fuel......% are achieved which is considerably higher than the conventional Combined Cycles (CC). Both ASR (Adiabatic Steam Reformer) and CPO (Catalytic Partial Oxidation) fuel pre-reformer reactors are considered in this investigation....

Catalytic site identification—a web server to identify catalytic site structural matches throughout PDB

Science.gov (United States)

Kirshner, Daniel A.; Nilmeier, Jerome P.; Lightstone, Felice C.

2013-01-01

The catalytic site identification web server provides the innovative capability to find structural matches to a user-specified catalytic site among all Protein Data Bank proteins rapidly (in less than a minute). The server also can examine a user-specified protein structure or model to identify structural matches to a library of catalytic sites. Finally, the server provides a database of pre-calculated matches between all Protein Data Bank proteins and the library of catalytic sites. The database has been used to derive a set of hypothesized novel enzymatic function annotations. In all cases, matches and putative binding sites (protein structure and surfaces) can be visualized interactively online. The website can be accessed at http://catsid.llnl.gov. PMID:23680785

On the nanostructuring and catalytic promotion of intermediate temperature solid oxide fuel cell (IT-SOFC) cathodes

Science.gov (United States)

Serra, José M.; Buchkremer, Hans-Peter

Solid oxide fuel cells (SOFCs) are highly efficient energy converters for both stationary and mobile purposes. However, their market introduction still demands the reduction of manufacture costs and one possible way to reach this goal is the decrease of the operating temperatures, which entails the improvement of the cathode electrocatalytic properties. An ideal cathode material may have mixed ionic and electronic conductivity as well as proper catalytic properties. Nanostructuring and catalytic promotion of mixed conducting perovskites (e.g. La 0.58Sr 0.4Fe 0.8Co 0.2O 3- δ) seem to be promising approaches to overcoming cathode polarization problems and are briefly illustrated here. The preparation of nanostructured cathodes with relatively high surface area and enough thermal stability enables to improve the oxygen exchange rate and therefore the overall SOFC performance. A similar effect was obtained by catalytic promoting the perovskite surface, allowing decoupling the catalytic and ionic-transport properties in the cathode design. Noble metal incorporation may improve the reversibility of the reduction cycles involved in the oxygen reduction. Under the cathode oxidizing conditions, Pd seems to be partially dissolved in the perovskite structure and as a result very well dispersed.

Fuel Flexible, Low Emission Catalytic Combustor for Opportunity Fuel Applications

Energy Technology Data Exchange (ETDEWEB)

Eteman, Shahrokh

2013-06-30

Limited fuel resources, increasing energy demand and stringent emission regulations are drivers to evaluate process off-gases or process waste streams as fuels for power generation. Often these process waste streams have low energy content and/or highly reactive components. Operability of low energy content fuels in gas turbines leads to issues such as unstable and incomplete combustion. On the other hand, fuels containing higher-order hydrocarbons lead to flashback and auto-ignition issues. Due to above reasons, these fuels cannot be used directly without modifications or efficiency penalties in gas turbine engines. To enable the use of these wide variety of fuels in gas turbine engines a rich catalytic lean burn (RCL®) combustion system was developed and tested in a subscale high pressure (10 atm.) rig. The RCL® injector provided stability and extended turndown to low Btu fuels due to catalytic pre-reaction. Previous work has shown promise with fuels such as blast furnace gas (BFG) with LHV of 85 Btu/ft3 successfully combusted. This program extends on this work by further modifying the combustor to achieve greater catalytic stability enhancement. Fuels containing low energy content such as weak natural gas with a Lower Heating Value (LHV) of 6.5 MJ/m3 (180 Btu/ft3 to natural gas fuels containing higher hydrocarbon (e.g ethane) with LHV of 37.6 MJ/m3 (1010 Btu/ft3) were demonstrated with improved combustion stability; an extended turndown (defined as the difference between catalytic and non-catalytic lean blow out) of greater than 250oF was achieved with CO and NOx emissions lower than 5 ppm corrected to 15% O2. In addition, for highly reactive fuels the catalytic region preferentially pre-reacted the higher order hydrocarbons with no events of flashback or auto-ignition allowing a stable and safe operation with low NOx and CO emissions.

The development of catalytic nucleophilic additions of terminal alkynes in water.

Science.gov (United States)

Li, Chao-Jun

2010-04-20

One of the major research endeavors in synthetic chemistry over the past two decades is the exploration of synthetic methods that work under ambient atmosphere with benign solvents, that maximize atom utilization, and that directly transform natural resources, such as renewable biomass, from their native states into useful chemical products, thus avoiding the need for protecting groups. The nucleophilic addition of terminal alkynes to various unsaturated electrophiles is a classical (textbook) reaction in organic chemistry, allowing the formation of a C-C bond while simultaneously introducing the alkyne functionality. A prerequisite of this classical reaction is the stoichiometric generation of highly reactive metal acetylides. Over the past decade, our laboratory and others have been exploring an alternative, the catalytic and direct nucleophilic addition of terminal alkynes to unsaturated electrophiles in water. We found that various terminal alkynes can react efficiently with a wide range of such electrophiles in water (or organic solvent) in the presence of simple and readily available catalysts, such as copper, silver, gold, iron, palladium, and others. In this Account, we describe the development of these synthetic methods, focusing primarily on results from our laboratory. Our studies include the following: (i) catalytic reaction of terminal alkynes with acid chloride, (ii) catalytic addition of terminal alkynes to aldehydes and ketones, (iii) catalytic addition of alkynes to C=N bonds, and (iv) catalytic conjugate additions. Most importantly, these reactions can tolerate various functional groups and, in many cases, perform better in water than in organic solvents, clearly defying classical reactivities predicated on the relative acidities of water, alcohols, and terminal alkynes. We further discuss multicomponent and enantioselective reactions that were developed. These methods provide an alternative to the traditional requirement of separate steps in

Cell cycle-specific UNG2 phosphorylations regulate protein turnover, activity and association with RPA

DEFF Research Database (Denmark)

Hagen, Lars; Kavli, Bodil; Sousa, Mirta M L

2008-01-01

-catalytic domain that confer distinct functional properties to UNG2. These are apparently generated by cyclin-dependent kinases through stepwise phosphorylation of S23, T60 and S64 in the cell cycle. Phosphorylation of S23 in late G1/early S confers increased association with replication protein A (RPA......) and replicating chromatin and markedly increases the catalytic turnover of UNG2. Conversely, progressive phosphorylation of T60 and S64 throughout S phase mediates reduced binding to RPA and flag UNG2 for breakdown in G2 by forming a cyclin E/c-myc-like phosphodegron. The enhanced catalytic turnover of UNG2 p-S23...

Direct catalytic transformation of carbohydrates into 5-ethoxymethylfurfural with acid–base bifunctional hybrid nanospheres

International Nuclear Information System (INIS)

Li, Hu; Govind, Khokarale Santosh; Kotni, Ramakrishna; Shunmugavel, Saravanamurugan; Riisager, Anders; Yang, Song

2014-01-01

Graphical abstract: Catalytic conversion of carbohydrates into HMF and EMF in ethanol/DMSO with acid–base bifunctional hybrid nanospheres prepared from self-assembly of corresponding basic amino acids and HPA. - Highlights: • Acid–base bifunctional nanospheres were efficient for production of EMF from sugars. • Synthesis of EMF in a high yield of 76.6% was realized from fructose. • Fructose based biopolymers could also be converted into EMF with good yields. • Ethyl glucopyranoside was produced in good yields from glucose in ethanol. - Abstract: A series of acid–base bifunctional hybrid nanospheres prepared from the self-assembly of basic amino acids and phosphotungstic acid (HPA) with different molar ratios were employed as efficient and recyclable catalysts for synthesis of liquid biofuel 5-ethoxymethylfurfural (EMF) from various carbohydrates. A high EMF yield of 76.6%, 58.5%, 42.4%, and 36.5% could be achieved, when fructose, inulin, sorbose, and sucrose were used as starting materials, respectively. Although, the acid–base bifunctional nanocatalysts were inert for synthesis of EMF from glucose based carbohydrates, ethyl glucopyranoside in good yields could be obtained from glucose in ethanol. Moreover, the nanocatalyst functionalized with acid and basic sites was able to be reused several times with no significant loss in catalytic activity

Thermodynamic characteristics of a low concentration methane catalytic combustion gas turbine

International Nuclear Information System (INIS)

Yin, Juan; Su, Shi; Yu, Xin Xiang; Weng, Yiwu

2010-01-01

Low concentration methane, emitted from coal mines, landfill, animal waste, etc. into the atmosphere, is not only a greenhouse gas, but also a waste energy source if not utilised. Methane is 23 times more potent than CO 2 in terms of trapping heat in the atmosphere over a timeframe of 100 years. This paper studies a novel lean burn catalytic combustion gas turbine, which can be powered with about 1% methane (volume) in air. When this technology is successfully developed, it can be used not only to mitigate the methane for greenhouse gas reduction, but also to utilise such methane as a clean energy source. This paper presents our study results on the thermodynamic characteristics of this new lean burn catalytic combustion gas turbine system by conducting thermal performance analysis of the turbine cycle. The thermodynamic data including thermal efficiencies and exergy loss of main components of the turbine system are presented under different pressure ratios, turbine inlet temperatures and methane concentrations.

Directed modification of L-LcLDH1, an L-lactate dehydrogenase from Lactobacillus casei, to improve its specific activity and catalytic efficiency towards phenylpyruvic acid.

Science.gov (United States)

Li, Jian-Fang; Li, Xue-Qing; Liu, Yan; Yuan, Feng-Jiao; Zhang, Ting; Wu, Min-Chen; Zhang, Ji-Ru

2018-05-22

To improve the specific activity and catalytic efficiency of L-LcLDH1, an NADH-dependent allosteric L-lactate dehydrogenase from L. casei, towards phenylpyruvic acid (PPA), its directed modification was conducted based on the semi-rational design. The three variant genes, Lcldh1 Q88R , Lcldh1 I229A and Lcldh1 T235G , were constructed by whole-plasmid PCR as designed theoretically, and expressed in E. coli BL21(DE3), respectively. The purified mutant, L-LcLDH1 Q88R or L-LcLDH1 I229A , displayed the specific activity of 451.5 or 512.4 U/mg towards PPA, by which the asymmetric reduction of PPA afforded L-phenyllactic acid (PLA) with an enantiomeric excess (ee p ) more than 99%. Their catalytic efficiencies (k cat /K m ) without D-fructose-1,6-diphosphate (D-FDP) were 4.8- and 5.2-fold that of L-LcLDH1. Additionally, the k cat /K m values of L-LcLDH1 Q88R and L-LcLDH1 I229A with D-FDP were 168.4- and 8.5-fold higher than those of the same enzymes without D-FDP, respectively. The analysis of catalytic mechanisms by molecular docking (MD) simulation indicated that substituting I229 in L-LcLDH1 with Ala enlarges the space of substrate-binding pocket, and that the replacement of Q88 with Arg makes the inlet of pocket larger than that of L-LcLDH1. Copyright © 2018 Elsevier B.V. All rights reserved.

A direct estimate of evapotranspiration over the Amazon basin and implications for our understanding of carbon and water cycling

Science.gov (United States)

Swann, A. L. S.; Koven, C.; Lombardozzi, D.; Bonan, G. B.

2017-12-01

Evapotranspiration (ET) is a critical term in the surface energy budget as well as the water cycle. There are few direct measurements of ET, and thus the magnitude and variability is poorly constrained at large spatial scales. Estimates of the annual cycle of ET over the Amazon are critical because they influence predictions of the seasonal cycle of carbon fluxes, as well as atmospheric dynamics and circulation. We estimate ET for the Amazon basin using a water budget approach, by differencing rainfall, discharge, and time-varying storage from the Gravity Recovery and Climate Experiment. We find that the climatological annual cycle of ET over the Amazon basin upstream of Óbidos shows suppression of ET during the wet season, and higher ET during the dry season, consistent with flux tower based observations in seasonally dry forests. We also find a statistically significant decrease in ET over the time period 2002-2015 of -1.46 mm/yr. Our direct estimate of the seasonal cycle of ET is largely consistent with previous indirect estimates, including energy budget based approaches, an up-scaled station based estimate, and land surface model estimates, but suggests that suppression of ET during the wet season is underestimated by existing products. We further quantify possible contributors to the phasing of the seasonal cycle and downward time trend using land surface models.

A Hybrid Catalytic Route to Fuels from Biomass Syngas

Energy Technology Data Exchange (ETDEWEB)

Harmon, Laurel [LanzaTech, Inc., Skokie, IL (United States); Hallen, Richard [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Lilga, Michael [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Heijstra, Bjorn [LanzaTech, Inc., Skokie, IL (United States); Palou-Rivera, Ignasi [LanzaTech, Inc., Skokie, IL (United States); Handler, Robert [Michigan Technological Univ., Houghton, MI (United States)

2017-12-31

feed, syngas composition, and impurities. Ethanol feedstocks from all three types of biomass were demonstrated to be comparable to grain derived ethanol and suitable for the LT-PNNL ATJ process. The LT-PNNL ATJ catalytic upgrading process was demonstrated at lab scale for over 2000 hours of continuous operation on a single catalyst load. LanzaTech scaled up the ATJ process, producing 4000 gallons of jet and 600 gallons of diesel for testing and a future proving flight. The LT-PNNL ATJ process, at lab and pilot scale, using commercial grain-based ethanol and steel mill waste gas-based ethanol (“Lanzanol”), produces high-quality fuel-range distillates containing primarily normal paraffins and isoparaffins. The LT-PNNL ATJ fuel has equivalent properties to previously-approved SPKs such as F-T, HEFA, and ATJ from isobutanol, and conforms with critical properties needed to blend with conventional jet fuel. The project showed that the 2,3-BDO fermentation co-product can be separated economically utilizing Simulated Moving Bed (SMB) technology. 2,3-BDO can be catalytically converted to 1,3-butadiene (BD) in a two-step process with at least 70% yield, producing a chemical intermediate suitable for downstream applications. Technoeconomic and life cycle analyses of the biomass to jet process with and without 2,3-BDO production showed that capital costs are sensitive to the proportion of the 2,3-BDO co-product and biomass feedstock. The co-product 2,3-BDO, converted through to BD, significantly reduces the cash cost of production of the hydrocarbon fuels. Life cycle GHG emissions of ATJ SPK produced from biomass using a steam gasification system are projected to be significantly lower than those of conventional jet fuel. The project demonstrated that a high quality ATJ SPK, can be produced from biomass via a hybrid gas fermentation/catalytic route. Validation of the LT-PNNL ATJ process using a variety of ethanol feedstocks demonstrated the viability of a future model of

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

Science.gov (United States)

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.

Mid-Term Direction of JAEA Nuclear Fuel Cycle Engineering Laboratories

International Nuclear Information System (INIS)

Ojima, H.; Sugiyama, T.; Tanaka, K.; Takeda, S.; Nomura, S.

2009-01-01

1. Introduction Nuclear Fuel Cycle Engineering Laboratories (NCL) of Japan Atomic Energy Agency (JAEA) has sufficient experience and ability through its 50 year operation to establish the next generation closed cycle. It strives to become a world-class Center Of Excellence. 2. Current activity in NCL: 1) - Recycling of MOX fuel: The Tokai Reprocessing Plant has reprocessed 29 tons of MOX fuel from the ATR Fugenh as a part of 1140 tons of cumulative spent fuel reprocessed. JAEA has supported the pre-operation of the Rokkasho Reprocessing Plant. An innovative MOX pellet fabrication process has been developed in the Plutonium Fuel Development Center, and a part of products obtained by the development are used as a fuel for core confirmation test for re-startup of the FBR Monjuh. Characterization of MOX containing Am and Np has been studied and a new data such as melting point and thermal conductivity were reported. In the Chemical Processing Facility, a hot lab., an advanced aqueous reprocessing technology has been tested for TRU recovery, economical improvement, etc., using irradiated MOX fuel from the FR Joyoh. 2) - Supporting Activity: JAEA has improved the effectiveness and efficiency of existing safeguards activities. The Integrated Safeguards approach for all facilities in NCL has been implemented since August, 2008, as a pioneer and a good example in the world. To reduce anxiety among local residents, NCL has explained its operation plans and exchanged information and opinions with them concerning potential risks to health and environment. Recently, stake-holder participation in the management of NCL was started from the view point of Corporate Social Responsibility. In April, 2008, the agreement was signed with Idaho National Laboratory for cooperation of personnel training in fuel cycle area. 3. Mid-Term Direction: In Japan, feasibility and direction of the transition period from the LWR era to the FBR era should be discussed for the next several years. Study

Mid-Term Direction of JAEA Nuclear Fuel Cycle Engineering Laboratories

Energy Technology Data Exchange (ETDEWEB)

Ojima, H.; Sugiyama, T.; Tanaka, K.; Takeda, S.; Nomura, S. [Tokai-mura, Ibaraki-ken 319-1194 (Japan)

2009-06-15

1. Introduction Nuclear Fuel Cycle Engineering Laboratories (NCL) of Japan Atomic Energy Agency (JAEA) has sufficient experience and ability through its 50 year operation to establish the next generation closed cycle. It strives to become a world-class Center Of Excellence. 2. Current activity in NCL: 1) - Recycling of MOX fuel: The Tokai Reprocessing Plant has reprocessed 29 tons of MOX fuel from the ATR Fugenh as a part of 1140 tons of cumulative spent fuel reprocessed. JAEA has supported the pre-operation of the Rokkasho Reprocessing Plant. An innovative MOX pellet fabrication process has been developed in the Plutonium Fuel Development Center, and a part of products obtained by the development are used as a fuel for core confirmation test for re-startup of the FBR Monjuh. Characterization of MOX containing Am and Np has been studied and a new data such as melting point and thermal conductivity were reported. In the Chemical Processing Facility, a hot lab., an advanced aqueous reprocessing technology has been tested for TRU recovery, economical improvement, etc., using irradiated MOX fuel from the FR Joyoh. 2) - Supporting Activity: JAEA has improved the effectiveness and efficiency of existing safeguards activities. The Integrated Safeguards approach for all facilities in NCL has been implemented since August, 2008, as a pioneer and a good example in the world. To reduce anxiety among local residents, NCL has explained its operation plans and exchanged information and opinions with them concerning potential risks to health and environment. Recently, stake-holder participation in the management of NCL was started from the view point of Corporate Social Responsibility. In April, 2008, the agreement was signed with Idaho National Laboratory for cooperation of personnel training in fuel cycle area. 3. Mid-Term Direction: In Japan, feasibility and direction of the transition period from the LWR era to the FBR era should be discussed for the next several years. Study

Patterned self-assembled monolayers for nanoscale lithography and the control of catalytically produced electroosmosis

Science.gov (United States)

Subramanian, Shyamala

This thesis explores two applications of self-assembled monolayers (SAMs) (a) for developing novel molecular assembly based nanolithography techniques and (b) for tailoring zeta-potential of surfaces towards achieving directional control of catalytically induced fluid flow. The first half of the thesis develops the process of molecular ruler lithography using sacrificial host structures. This is a novel hybrid nanolithography technique which combines chemical self-assembly with conventional fabrication methods for improving the resolution of existing lithography tools to sub-50 nm. Previous work related to molecular ruler lithography have shown the use of thiol-SAMs, placed one on top of the other like a molecular resist, for scaling down feature sizes. In this thesis various engineering solutions for improving the reproducibility, yield, nanoscale roughness and overall manufacturability of the process are introduced. This is achieved by introducing a sacrificial inert layer underneath the gold parent structure. This bilayer sacrificial host allows for preferential, easy and quick removal of the parent structures, isolates the parent metal from the underlying substrate and improves reproducibility of the lift-off process. Also it opens avenues for fabrication of high aspect ratio features. Also molecular layer vapor deposition method is developed for building the multilayer molecular resist via vapor phase to reduce contaminations and yield issues associated with solution phase deposition. The smallest isolated metal features produced using this process were 40 nm in width. The second half of the thesis describes application of thiol-SAMs to tailor surface properties of gold, specifically the surface charge or zeta potential. Previous work has demonstrated that the direction of movement of fluid in the vicinity of a catalytically active bimetallic junction placed in a solution of dilute hydrogen peroxide depends on the charge of the gold surface. SAMs with

Optical manipulation and catalytic activity enhanced by surface plasmon effect

Science.gov (United States)

Zou, Ningmu; Min, Jiang; Jiao, Wenxiang; Wang, Guanghui

2017-02-01

For optical manipulation, a nano-optical conveyor belt consisting of an array of gold plasmonic non-concentric nano-rings (PNNRs) is demonstrated for the realization of trapping and unidirectional transportation of nanoparticles by polarization rotation of excitation beam. These hot spots of an asymmetric plasmonic nanostructure are polarization dependent, therefore, one can use the incident polarization state to manipulate the trapped targets. Trapped particles could be transferred between adjacent PNNRs in a given direction just by rotating the polarization of incident beam due to unbalanced potential. The angular dependent distribution of electric field around PNNR has been solved using the three- dimensional finite-difference time-domain (FDTD) technique. For optical enhanced catalytic activity, the spectral properties of dimers of Au nanorod-Au nanorod nanostructures under the excitation of 532nm photons have been investigated. With a super-resolution catalytic mapping technique, we identified the existence of "hot spot" in terms of catalytic reactivity at the gap region within the twined plasmonic nanostructure. Also, FDTD calculation has revealed an intrinsic correlation between hot electron transfer.

Thermodynamic analysis of an integrated solid oxide fuel cell cycle with a rankine cycle

International Nuclear Information System (INIS)

Rokni, Masoud

2010-01-01

Hybrid systems consisting of solid oxide fuel cells (SOFC) on the top of a steam turbine (ST) are investigated. The plants are fired by natural gas (NG). A desulfurization reactor removes the sulfur content in the fuel while a pre-reformer breaks down the heavier hydro-carbons. The pre-treated fuel enters then into the anode side of the SOFC. The remaining fuels after the SOFC stacks enter a burner for further burning. The off-gases are then used to produce steam for a Rankine cycle in a heat recovery steam generator (HRSG). Different system setups are suggested. Cyclic efficiencies up to 67% are achieved which is considerably higher than the conventional combined cycles (CC). Both adiabatic steam reformer (ASR) and catalytic partial oxidation (CPO) fuel pre-reformer reactors are considered in this investigation.

Direct in situ observations of single Fe atom catalytic processes and anomalous diffusion at graphene edges

Science.gov (United States)

Zhao, Jiong; Deng, Qingming; Avdoshenko, Stanislav M.; Fu, Lei; Eckert, Jürgen; Rümmeli, Mark H.

2014-01-01

Single-atom catalysts are of great interest because of their high efficiency. In the case of chemically deposited sp2 carbon, the implementation of a single transition metal atom for growth can provide crucial insight into the formation mechanisms of graphene and carbon nanotubes. This knowledge is particularly important if we are to overcome fabrication difficulties in these materials and fully take advantage of their distinct band structures and physical properties. In this work, we present atomically resolved transmission EM in situ investigations of single Fe atoms at graphene edges. Our in situ observations show individual iron atoms diffusing along an edge either removing or adding carbon atoms (viz., catalytic action). The experimental observations of the catalytic behavior of a single Fe atom are in excellent agreement with supporting theoretical studies. In addition, the kinetics of Fe atoms at graphene edges are shown to exhibit anomalous diffusion, which again, is in agreement with our theoretical investigations. PMID:25331874

Partial catalytic oxidation of CH{sub 4} to synthesis gas for power generation - Final report

Energy Technology Data Exchange (ETDEWEB)

Mantzaras, I.; Schneider, A.

2006-03-15

The partial oxidation of methane to synthesis gas over rhodium catalysts has been investigated experimentally and numerically in the pressure range of 4 to 10 bar. The methane/oxidizer feed has been diluted with large amounts of H{sub 2}O and CO{sub 2} (up to 70% vol.) in order to simulate new power generation cycles with large exhaust gas recycle. Experiments were carried out in an optically accessible channel-flow reactor that facilitated laser-based in situ measurements, and also in a subscale gas-turbine catalytic reactor. Full-elliptic steady and transient two-dimensional numerical codes were used, which included elementary hetero-/homogeneous chemical reaction schemes. The following are the key conclusions: a) Heterogeneous (catalytic) and homogeneous (gas-phase) schemes have been validated for the partial catalytic oxidation of methane with large exhaust gas recycle. b) The impact of added H{sub 2}O and CO{sub 2} has been elucidated. The added H{sub 2}O increased the methane conversion and hydrogen selectivity, while it decreased the CO selectivity. The chemical impact of CO{sub 2} (dry reforming) was minimal. c) The numerical model reproduced the measured catalytic ignition times. It was further shown that the chemical impact of H{sub 2}O and CO{sub 2} on the catalytic ignition delay times was minimal. d) The noble metal dispersion increased with different support materials, in the order Rh/{alpha}-Al{sub 2}O{sub 3}, Rh/ZrO{sub 2}, and Rh/Ce-ZrO{sub 2}. An evident relationship was established between the noble metal dispersion and the catalytic behavior. (authors)

The DNA topoisomerase II catalytic inhibitor merbarone is genotoxic and induces endoreduplication

International Nuclear Information System (INIS)

Pastor, Nuria; Domínguez, Inmaculada; Orta, Manuel Luís; Campanella, Claudia; Mateos, Santiago; Cortés, Felipe

2012-01-01

In the last years a number of reports have shown that the so-called topoisomerase II (topo II) catalytic inhibitors are able to induce DNA and chromosome damage, an unexpected result taking into account that they do not stabilize topo II-DNA cleavable complexes, a feature of topo II poisons such as etoposide and amsacrine. Merbarone inhibits the catalytic activity of topo II by blocking DNA cleavage by the enzyme. While it was first reported that merbarone does not induce genotoxic effects in mammalian cells, this has been challenged by reports showing that the topo II inhibitor induces efficiently chromosome and DNA damage, and the question as to a possible behavior as a topo II poison has been put forward. Given these contradictory results, and the as yet incomplete knowledge of the molecular mechanism of action of merbarone, in the present study we have tried to further characterize the mechanism of action of merbarone on cell proliferation, cell cycle, as well as chromosome and DNA damage in cultured CHO cells. Merbarone was cytotoxic as well as genotoxic, inhibited topo II catalytic activity, and induced endoreduplication. We have also shown that merbarone-induced DNA damage depends upon ongoing DNA synthesis. Supporting this, inhibition of DNA synthesis causes reduction of DNA damage and increased cell survival.

Effect of support on the catalytic activity of manganese oxide catalyts for toluene combustion

International Nuclear Information System (INIS)

Pozan, Gulin Selda

2012-01-01

Highlights: ► α-Al 2 O 3 , obtained from Bohmite, as a support for enhancing of the activity. ► The support material for catalytic oxidation. ► The manganese state and oxygen species effect on the catalytic combustion reaction. - Abstract: The aim of this work was to study combustion of toluene (1000 ppm) over MnO 2 modified with different supports. α-Al 2 O 3 and γ-Al 2 O 3 obtained from Boehmite, γ-Al 2 O 3 (commercial), SiO 2 , TiO 2 and ZrO 2 were used as commercial support materials. In view of potential interest of this process, the influence of support material on the catalytic performance was discussed. The deposition of 9.5MnO 2 was performed by impregnation over support. The catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature programmed reduction and oxidation (TPR/TPO) and thermogravimetric analysis (TGA). The catalytic tests were carried out at atmospheric pressure in a fixed-bed flow reactor. 9.5MnO 2 /α-Al 2 O 3 (B) (synthesized from Boehmite) catalyst exhibits the highest catalytic activity, over which the toluene conversion was up to 90% at a temperature of 289 °C. Considering all the characterization and reaction data reported in this study, it was concluded that the manganese state and oxygen species played an important role in the catalytic activity.

In situ catalytic growth of large-area multilayered graphene/MoS2 heterostructures

Science.gov (United States)

Fu, Wei; Du, Fei-Hu; Su, Juan; Li, Xin-Hao; Wei, Xiao; Ye, Tian-Nan; Wang, Kai-Xue; Chen, Jie-Sheng

2014-04-01

Stacking various two-dimensional atomic crystals on top of each other is a feasible approach to create unique multilayered heterostructures with desired properties. Herein for the first time, we present a controlled preparation of large-area graphene/MoS2 heterostructures via a simple heating procedure on Mo-oleate complex coated sodium sulfate under N2 atmosphere. Through a direct in situ catalytic reaction, graphene layer has been uniformly grown on the MoS2 film formed by the reaction of Mo species with S pecies, which is from the carbothermal reduction of sodium sulfate. Due to the excellent graphene ``painting'' on MoS2 atomic layers, the significantly shortened lithium ion diffusion distance and the markedly enhanced electronic conductivity, these multilayered graphene/MoS2 heterostructures exhibit high specific capacity, unprecedented rate performance and outstanding cycling stability, especially at a high current density, when used as an anode material for lithium batteries. This work provides a simple but efficient route for the controlled fabrication of large-area multilayered graphene/metal sulfide heterostructures with promising applications in battery manufacture, electronics or catalysis.

Catalytic microtubular jet engines self-propelled by accumulated gas bubbles.

Science.gov (United States)

Solovev, Alexander A; Mei, Yongfeng; Bermúdez Ureña, Esteban; Huang, Gaoshan; Schmidt, Oliver G

2009-07-01

Strain-engineered microtubes with an inner catalytic surface serve as self-propelled microjet engines with speeds of up to approximately 2 mm s(-1) (approximately 50 body lengths per second). The motion of the microjets is caused by gas bubbles ejecting from one opening of the tube, and the velocity can be well approximated by the product of the bubble radius and the bubble ejection frequency. Trajectories of various different geometries are well visualized by long microbubble tails. If a magnetic layer is integrated into the wall of the microjet engine, we can control and localize the trajectories by applying external rotating magnetic fields. Fluid (i.e., fuel) pumping through the microtubes is revealed and directly clarifies the working principle of the catalytic microjet engines.

An Adaptor Domain-Mediated Auto-Catalytic Interfacial Kinase Reaction

Science.gov (United States)

Liao, Xiaoli; Su, Jing; Mrksich, Milan

2010-01-01

This paper describes a model system for studying the auto-catalytic phosphorylation of an immobilized substrate by a kinase enzyme. This work uses self-assembled monolayers (SAMs) of alkanethiolates on gold to present the peptide substrate on a planar surface. Treatment of the monolayer with Abl kinase results in phosphorylation of the substrate. The phosphorylated peptide then serves as a ligand for the SH2 adaptor domain of the kinase and thereby directs the kinase activity to nearby peptide substrates. This directed reaction is intramolecular and proceeds with a faster rate than does the initial, intermolecular reaction, making this an auto-catalytic process. The kinetic non-linearity gives rise to properties that have no counterpart in the corresponding homogeneous phase reaction: in one example, the rate for phosphorylation of a mixture of two peptides is faster than the sum of the rates for phosphorylation of each peptide when presented alone. This work highlights the use of an adaptor domain in modulating the activity of a kinase enzyme for an immobilized substrate and offers a new approach for studying biochemical reactions in spatially inhomogeneous settings. PMID:19821459

Plant accident dynamics of high-temperature reactors with direct gas turbine cycle

International Nuclear Information System (INIS)

Waloch, M.L.

1977-01-01

In the paper submitted, a one-dimensional accident simulation model for high-temperature reactors with direct-cycle gas turbine (single-cycle facilities) is described. The paper assesses the sudden failure of a gas duct caused by the double-ended break of one out of several parallel pipes before and behind the reactor for a non-integrated plant, leading to major loads in the reactor region, as well as the complete loss of vanes of the compressor for an integrated plant. The results of the calculations show especially high loads for the break of a hot-gas pipe immediately behind the flow restrictors of the reactor outlet, because of prolonged effects of pressure gradients in the reactor region and the maximum core differential pressure. A plant accident dynamics calculation therefore allows to find a compromise between the requirements of stable compressor operation, on the one hand, and small loads in the reactor in the course of an accident, on the other, by establishing in a co-ordinated manner the narrowing ratio of the flow restrictors. (GL) [de

MoS2 nanosheets direct supported on reduced graphene oxide: An advanced electrocatalyst for hydrogen evolution reaction.

Directory of Open Access Journals (Sweden)

Jiamu Cao

Full Text Available Molybdenum disulfide nanosheets/reduced graphene oxide (MoS2 NSs/rGO nanohybrid as a highly effective catalyst for hydrogen evolution reaction (HER have been successfully synthesized by a facile microwave-assisted method. The results clearly reveal that direct grown of MoS2 NSs on rGO have been achieved. Electrochemical tests show that the as-prepared hybrid material exhibited excellent HER activity, with a small Tafel slope of 57 mV dec-1, an overpotential of 130 mV and remarkable cycling stability. After analysis, the observed outstanding catalytic performance can be attributed to the uniform distribution of the MoS2 NSs, which are characterized by the presence of multiple active sites as well as the effective electron transport route provided by the conductive rGO substrate. Moreover, according to the classic theory, the mechanism governing of the catalytic HER on the MoS2 NSs/rGO nanohybrid has been clarified.

Analysis of a BWR direct cycle forced circulation power plants operation

International Nuclear Information System (INIS)

Andrade, G.G. de.

1973-01-01

First, it is established a general view over the operational problems of the BWR direct cycle forced circulation power plants, and then it is analysed the possibility of the utilization of the energy purged from the turbine as an additional energy for the electrical generation. To simulate the BWR power plant and to obtain the solution of the mathematical model it was developed a computer code named ATOR which shows the feasibility of the proposed method. In this way it is shown the possibility to get a better maneuvering allowance for the BWR power plant whenever it is permitted a convenient use of the vapor extracted from the turbine for the feedwater pre-heaters of the reactor. (author)

Fabrication of palladium nanoparticles immobilized on an amine-functionalized ceramic membrane support using a nanoparticulate colloidal impregnation method with enhanced catalytic properties

Energy Technology Data Exchange (ETDEWEB)

Du, Yan; Chen, Rizhi [Nanjing Tech University, Nanjing (China)

2015-09-15

An efficient and reusable catalyst was developed by depositing palladium nanoparticles on an amine-functionalized ceramic membrane support using a nanoparticulate colloidal impregnation method. The as-prepared Pdloaded ceramic membrane support was characterized by XRD, SEM, EDS, TEM, XPS, ICP, and its catalytic properties were investigated in the liquid-phase p-nitrophenol hydrogenation. A comparative study was also made with the palladium nanoparticles deposited on an amine-functionalized ceramic membrane support by an impregnation-reduction method. The palladium nanoparticles could be homogeneously immobilized on the ceramic membrane support surface, and exhibited excellent catalytic performance in the p-nitrophenol hydrogenation. The catalytic activity of the Pdloaded ceramic membrane support prepared by the nanoparticulate colloidal impregnation method increased by 16.6% compared to that of impregnation-reduction method. In the nanoparticulate colloidal impregnation method, palladium nanoparticles were presynthesized, higher loading of Pd(0) could be obtained, resulting in better catalytic activity. The as-prepared Pd-loaded ceramic membrane support could be easily reused for several cycles without appreciable degradation of catalytic activity.

On acyclicity of games with cycles

DEFF Research Database (Denmark)

Andersson, Klas Olof Daniel; Hansen, Thomas Dueholm; Gurvich, Vladimir

2010-01-01

We study restricted improvement cycles (ri-cycles) in finite positional n-person games with perfect information modeled by directed graphs (di-graphs) that may contain directed cycles (di-cycles). We assume that all these di-cycles form one outcome c, for example, a draw. We obtain criteria...

Bearing compartment seal systems for turbomachinery in direct-cycle HTGR power plants

International Nuclear Information System (INIS)

Adams, R.G.; Boenig, F.H.; Pfeifer, G.D.

1977-10-01

The direct-cycle High-Temperature Gas-Cooled Reactor (HTGR) employs a closed gas-turbine cycle with the primary reactor coolant (helium) as the working fluid. Design studies on this type of plant, carried out since 1971, have demonstrated, among other points, the advantages of the integrated arrangement, in which power from the cycle is transmitted to the electric generators by turbomachines completely enclosed in the reactor pressure vessel. A result of this arrangement is that the bearings are entirely enclosed within the primary coolant system of the reactor. An important aspect of the design of the turbomachinery is its prevention or minimization of the ingress of lubricants into the primary coolant system and its prevention of ingress of primary coolant into the bearing compartments. The design studies, which included thorough conceptual designs of the turbomachinery with emphasis on bearings and seals and their support systems showed that total exclusion of lubricant requires extremely complex seals and seal support systems. The variation of system low-end pressure with control actuation and the requirement that the bearing cavity pressure follow these variations were proved to further complicate the service system. The tolerance of even relatively minute amounts of entering lubricant during control transients will allow considerable simplification. This paper discusses the above-mentioned problems and their solutions in tracing the design evolution of a satisfactory bearing-compartment seals and service system. The resulting system appears to be feasible on the basis of experience with industrial gas turbines

Prospects of power conversion technology of direct-cycle helium gas turbine for MHTGR

International Nuclear Information System (INIS)

Li Yong; Zhang Zuoyi

1999-01-01

The modular high temperature gas cooled reactor (MHTGR) is a modern passively safe reactor. The reactor and helium gas turbine may be combined for high efficiency's power conversion, because MHTGR has high outlet temperature up to 950 degree C. Two different schemes are planed separately by USA and South Africa. the helium gas turbine methodologies adopted by them are mainly based on the developed heavy duty industrial and aviation gas turbine technology. The author introduces the differences of two technologies and some design issues in the design and manufacture. Moreover, the author conclude that directly coupling a closed Brayton cycle gas turbine concept to the passively safe MHTGR is the developing direction of MHTGR due to its efficiency which is much higher than that of using steam turbine

TEMPO functionalized C{sub 60} fullerene deposited on gold surface for catalytic oxidation of selected alcohols

Energy Technology Data Exchange (ETDEWEB)

Piotrowski, Piotr; Pawłowska, Joanna [University of Warsaw, Department of Chemistry (Poland); Sadło, Jarosław Grzegorz [Institute of Nuclear Chemistry and Technology (Poland); Bilewicz, Renata; Kaim, Andrzej, E-mail: akaim@chem.uw.edu.pl [University of Warsaw, Department of Chemistry (Poland)

2017-05-15

C{sub 60}TEMPO{sub 10} catalytic system linked to a microspherical gold support through a covalent S-Au bond was developed. The C{sub 60}TEMPO{sub 10}@Au composite catalyst had a particle size of 0.5–0.8 μm and was covered with the fullerenes derivative of 2.3 nm diameter bearing ten nitroxyl groups; the organic film showed up to 50 nm thickness. The catalytic composite allowed for the oxidation under mild conditions of various primary and secondary alcohols to the corresponding aldehyde and ketone analogues with efficiencies as high as 79–98%, thus giving values typical for homogeneous catalysis, while retaining at the same time all the advantages of heterogeneous catalysis, e.g., easy separation by filtration from the reaction mixture. The catalytic activity of the resulting system was studied by means of high pressure liquid chromatography. A redox mechanism was proposed for the process. In the catalytic cycle of the oxidation process, the TEMPO moiety was continuously regenerated in situ with an applied primary oxidant, for example, O{sub 2}/Fe{sup 3+} system. The new intermediate composite components and the final catalyst were characterized by various spectroscopic methods and thermogravimetry.

Non-catalytic direct synthesis of graphene on Si (111) wafers by using inductively-coupled plasma chemical vapor deposition

Science.gov (United States)

Hwang, Sung Won; Shin, Hyunho; Lee, Bongsoo; Choi, Suk-Ho

2016-08-01

We employ inductively-coupled plasma chemical vapor deposition for non-catalytic growth of graphene on a Si (111) wafer or glass substrate, which is useful for practical device applications of graphene without transfer processes. At a RF power (P) of 500 W under C2H2 flow, defect-free 3 ˜ 5-layer graphene is grown on Si (111) wafers, but on glass substrate, the layer is thicker and defective, as characterized by Raman spectroscopy and electron microscopy. The graphene is produced on Si (111) for P down to 190 W whereas it is almost not formed on glass for P < 250 W, possibly resulting from the weak catalytic-reaction-like effect on glass. These results are discussed based on possible growth mechanisms.

Promotion and Suppression of Centriole Duplication Are Catalytically Coupled through PLK4 to Ensure Centriole Homeostasis

Directory of Open Access Journals (Sweden)

Minhee Kim

2016-08-01

Full Text Available PLK4 is the major kinase driving centriole duplication. Duplication occurs only once per cell cycle, forming one new (or daughter centriole that is tightly engaged to the preexisting (or mother centriole. Centriole engagement is known to block the reduplication of mother centrioles, but the molecular identity responsible for the block remains unclear. Here, we show that the centriolar cartwheel, the geometric scaffold for centriole assembly, forms the identity of daughter centrioles essential for the block, ceasing further duplication of the mother centriole to which it is engaged. To ensure a steady block, we found that the cartwheel requires constant maintenance by PLK4 through phosphorylation of the same substrate that drives centriole assembly, revealing a parsimonious control in which “assembly” and “block for new assembly” are linked through the same catalytic reaction to achieve homeostasis. Our results support a recently deduced model that the cartwheel-bound PLK4 directly suppresses centriole reduplication.

Pd(II)-Catalyzed Hydroxyl-Directed C–H Olefination Enabled by Mono-Protected Amino Acid Ligands

Science.gov (United States)

Lu, Yi; Wang, Dong-Hui; Engle, Keary M.

2010-01-01

A novel Pd(II)-catalyzed ortho-C–H olefination protocol has been developed using spatially remote, unprotected tertiary, secondary, and primary alcohols as the directing groups. Mono-N-protected amino acid ligands were found to promote the reaction, and an array of olefin coupling partners could be used. When electron-deficient alkenes were used, the resulting olefinated intermediates underwent subsequent Pd(II)-catalyzed oxidative intramolecular cyclization to give the corresponding pyran products, which could be converted into ortho-alkylated alcohols under hydrogenolysis conditions. The mechanistic details of the oxidative cyclization step are discussed and situated in the context of the overall catalytic cycle. PMID:20359184

Comparative Life Cycle Assessment of Lignocellulosic Ethanol Production: Biochemical Versus Thermochemical Conversion

Science.gov (United States)

Mu, Dongyan; Seager, Thomas; Rao, P. Suresh; Zhao, Fu

2010-10-01

Lignocellulosic biomass can be converted into ethanol through either biochemical or thermochemical conversion processes. Biochemical conversion involves hydrolysis and fermentation while thermochemical conversion involves gasification and catalytic synthesis. Even though these routes produce comparable amounts of ethanol and have similar energy efficiency at the plant level, little is known about their relative environmental performance from a life cycle perspective. Especially, the indirect impacts, i.e. emissions and resource consumption associated with the production of various process inputs, are largely neglected in previous studies. This article compiles material and energy flow data from process simulation models to develop life cycle inventory and compares the fossil fuel consumption, greenhouse gas emissions, and water consumption of both biomass-to-ethanol production processes. The results are presented in terms of contributions from feedstock, direct, indirect, and co-product credits for four representative biomass feedstocks i.e., wood chips, corn stover, waste paper, and wheat straw. To explore the potentials of the two conversion pathways, different technological scenarios are modeled, including current, 2012 and 2020 technology targets, as well as different production/co-production configurations. The modeling results suggest that biochemical conversion has slightly better performance on greenhouse gas emission and fossil fuel consumption, but that thermochemical conversion has significantly less direct, indirect, and life cycle water consumption. Also, if the thermochemical plant operates as a biorefinery with mixed alcohol co-products separated for chemicals, it has the potential to achieve better performance than biochemical pathway across all environmental impact categories considered due to higher co-product credits associated with chemicals being displaced. The results from this work serve as a starting point for developing full life cycle

Key parameters controlling the performance of catalytic motors

Energy Technology Data Exchange (ETDEWEB)

Esplandiu, Maria J.; Afshar Farniya, Ali [Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and The Barcelona Institute of Science and Technology, Campus UAB, Bellaterra, 08193 Barcelona (Spain); Reguera, David, E-mail: dreguera@ub.edu [Departament de Física Fonamental, Universitat de Barcelona, C/Martí i Franquès 1, 08028 Barcelona (Spain)

2016-03-28

The development of autonomous micro/nanomotors driven by self-generated chemical gradients is a topic of high interest given their potential impact in medicine and environmental remediation. Although impressive functionalities of these devices have been demonstrated, a detailed understanding of the propulsion mechanism is still lacking. In this work, we perform a comprehensive numerical analysis of the key parameters governing the actuation of bimetallic catalytic micropumps. We show that the fluid motion is driven by self-generated electro-osmosis where the electric field originates by a proton current rather than by a lateral charge asymmetry inside the double layer. Hence, the surface potential and the electric field are the key parameters for setting the pumping strength and directionality. The proton flux that generates the electric field stems from the proton gradient induced by the electrochemical reactions taken place at the pump. Surprisingly the electric field and consequently the fluid flow are mainly controlled by the ionic strength and not by the conductivity of the solution, as one could have expected. We have also analyzed the influence of the chemical fuel concentration, electrochemical reaction rates, and size of the metallic structures for an optimized pump performance. Our findings cast light on the complex chemomechanical actuation of catalytic motors and provide important clues for the search, design, and optimization of novel catalytic actuators.

Functional cooperation between FACT and MCM is coordinated with cell cycle and differential complex formation

Directory of Open Access Journals (Sweden)

Lin Chih-Li

2010-02-01

Full Text Available Abstract Background Functional cooperation between FACT and the MCM helicase complex constitutes an integral step during DNA replication initiation. However, mode of regulation that underlies the proper functional interaction of FACT and MCM is poorly understood. Methods & Results Here we present evidence indicating that such interaction is coordinated with cell cycle progression and differential complex formation. We first demonstrate the existence of two distinct FACT-MCM subassemblies, FACT-MCM2/4/6/7 and FACT-MCM2/3/4/5. Both complexes possess DNA unwinding activity and are subject to cell cycle-dependent enzymatic regulation. Interestingly, analysis of functional attributes further suggests that they act at distinct, and possibly sequential, steps during origin establishment and replication initiation. Moreover, we show that the phosphorylation profile of the FACT-associated MCM4 undergoes a cell cycle-dependent change, which is directly correlated with the catalytic activity of the FACT-MCM helicase complexes. Finally, at the quaternary structure level, physical interaction between FACT and MCM complexes is generally dependent on persistent cell cycle and further stabilized upon S phase entry. Cessation of mitotic cycle destabilizes the complex formation and likely leads to compromised coordination and activities. Conclusions Together, our results correlate FACT-MCM functionally and temporally with S phase and DNA replication. They further demonstrate that enzymatic activities intrinsically important for DNA replication are tightly controlled at various levels, thereby ensuring proper progression of, as well as exit from, the cell cycle and ultimately euploid gene balance.

ADVANCED BYPRODUCT RECOVERY: DIRECT CATALYTIC REDUCTION OF SO2 TO ELEMENTAL SULFUR

Energy Technology Data Exchange (ETDEWEB)

Robert S. Weber

1999-05-01

Arthur D. Little, Inc., together with its commercialization partner, Engelhard Corporation, and its university partner Tufts, investigated a single-step process for direct, catalytic reduction of sulfur dioxide from regenerable flue gas desulfurization processes to the more valuable elemental sulfur by-product. This development built on recently demonstrated SO{sub 2}-reduction catalyst performance at Tufts University on a DOE-sponsored program and is, in principle, applicable to processing of regenerator off-gases from all regenerable SO{sub 2}-control processes. In this program, laboratory-scale catalyst optimization work at Tufts was combined with supported catalyst formulation work at Engelhard, bench-scale supported catalyst testing at Arthur D. Little and market assessments, also by Arthur D. Little. Objectives included identification and performance evaluation of a catalyst which is robust and flexible with regard to choice of reducing gas. The catalyst formulation was improved significantly over the course of this work owing to the identification of a number of underlying phenomena that tended to reduce catalyst selectivity. The most promising catalysts discovered in the bench-scale tests at Tufts were transformed into monolith-supported catalysts at Engelhard. These catalyst samples were tested at larger scale at Arthur D. Little, where the laboratory-scale results were confirmed, namely that the catalysts do effectively reduce sulfur dioxide to elemental sulfur when operated under appropriate levels of conversion and in conditions that do not contain too much water or hydrogen. Ways to overcome those limitations were suggested by the laboratory results. Nonetheless, at the end of Phase I, the catalysts did not exhibit the very stringent levels of activity or selectivity that would have permitted ready scale-up to pilot or commercial operation. Therefore, we chose not to pursue Phase II of this work which would have included further bench-scale testing

Heterogeneous catalytic materials solid state chemistry, surface chemistry and catalytic behaviour

CERN Document Server

Busca, Guido

2014-01-01

Heterogeneous Catalytic Materials discusses experimental methods and the latest developments in three areas of research: heterogeneous catalysis; surface chemistry; and the chemistry of catalysts. Catalytic materials are those solids that allow the chemical reaction to occur efficiently and cost-effectively. This book provides you with all necessary information to synthesize, characterize, and relate the properties of a catalyst to its behavior, enabling you to select the appropriate catalyst for the process and reactor system. Oxides (used both as catalysts and as supports for cata

Comparison of FeS, FeS + S and solid superacid catalytic properties for coal hydro-liquefaction

Energy Technology Data Exchange (ETDEWEB)

Zhicai Wang; Hengfu Shui; Dexiang Zhang; Jinsheng Gao [East China University of Science and Technology, Shanghai (China). College of Resource and Environment Engineering

2007-03-15

Catalyst plays an important role in direct coal liquefaction. This paper focuses on the catalytic behavior of a novel SO{sub 4}{sup 2-}/ZrO{sub 2} superacid catalyst in coal hydro-liquefaction. A series of hydro-liquefaction experiments were conducted under mild conditions - 400{sup o}C, 30 min and H{sub 2} initial pressure 4 MPa in a batch autoclave with a volume of 100 ml. The catalytic property of SO{sub 4}{sup 2-}/ZrO{sub 2} was compared with FeS and FeS + S by Shenhua coal. The liquefaction products catalyzed by different catalysts were analyzed by FTIR spectrum, {sup 1}H NMR spectrum and element analysis. In addition, the SO{sub 4}{sup 2-}/ZrO{sub 2} solid superacid was characterized. The results indicated that the SO{sub 4}{sup 2-}/ZrO{sub 2} solid superacid shows outstanding catalytic property for direct liquefaction of coal and gives the highest coal conversion and gas + oil yield compared to other two catalysts. The THF conversion and the extraction yield of CS{sub 2}/NMP mixed solvent of liquefied coal catalyzed with SO{sub 4}{sup 2-}/ZrO{sub 2} are 76.3%, daf and 81.2%, daf respectively, and the yield of gas + oil is 62.5%, daf under the condition used in this study. The pyrolysis of coal macromolecular clusters can be promoted by catalysts such as FeS, FeS + S and SO{sub 4}{sup 2-}/ZrO{sub 2}. There may be only the pyrolysis of volatile matter and the relaxation of the structure of coal macromolecular clusters in non-catalytic liquefaction at 400{sup o}C. Added sulfur in FeS can improve the catalytic activity of hydrogenation. SO{sub 4}{sup 2-}/ZrO{sub 2} is a notable catalyst in the study of coal direct liquefaction because it shows excellent catalytic activities for the pyrolysis and the hydrogenation. In addition, it has been found that the C-O bond is the most stable group in coal liquefaction reaction except for the covalent bond between carbon and carbon. 34 refs., 6 figs., 6 tabs.

Effect of thermal cycling on the microstructure of a directionally solidified Fe, Cr, Al-TaC eutectic alloy

Science.gov (United States)

Harf, F. H.; Tewari, S. N.

1977-01-01

Cylindrical bars (1.2 cm diameter) of Fe-13.6Cr-3.7Al-9TaC (wt %) eutectic alloy were directionally solidified in a modified Bridgman type furnace at 1 cm/h. The alloy microstructure consisted of aligned TaC fibers imbedded in a bcc Fe-Cr-Al matrix. Specimens of the alloy were thermally cycled from 1100 to 425 C in a burner rig. The effects of 1800 thermal cycles on the microstructure was examined by scanning electron microscopy, revealing a zig-zag shape of TaC fibers aligned parallel to the growth direction. The mechanism of carbide solution and reprecipitation on the (111) easy growth planes, suggested previously to account for the development of irregular serrations in Co-Cr-Ni matrix alloys, is believed to be responsible for these zig-zag surfaces.

Long-Range Electrostatics-Induced Two-Proton Transfer Captured by Neutron Crystallography in an Enzyme Catalytic Site.

Science.gov (United States)

Gerlits, Oksana; Wymore, Troy; Das, Amit; Shen, Chen-Hsiang; Parks, Jerry M; Smith, Jeremy C; Weiss, Kevin L; Keen, David A; Blakeley, Matthew P; Louis, John M; Langan, Paul; Weber, Irene T; Kovalevsky, Andrey

2016-04-11

Neutron crystallography was used to directly locate two protons before and after a pH-induced two-proton transfer between catalytic aspartic acid residues and the hydroxy group of the bound clinical drug darunavir, located in the catalytic site of enzyme HIV-1 protease. The two-proton transfer is triggered by electrostatic effects arising from protonation state changes of surface residues far from the active site. The mechanism and pH effect are supported by quantum mechanics/molecular mechanics (QM/MM) calculations. The low-pH proton configuration in the catalytic site is deemed critical for the catalytic action of this enzyme and may apply more generally to other aspartic proteases. Neutrons therefore represent a superb probe to obtain structural details for proton transfer reactions in biological systems at a truly atomic level. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Extended Impact of Pin1 Catalytic Loop Phosphorylation Revealed by S71E Phosphomimetic.

Science.gov (United States)

Mahoney, Brendan J; Zhang, Meiling; Zintsmaster, John S; Peng, Jeffrey W

2018-03-02

Pin1 is a two-domain human protein that catalyzes the cis-trans isomerization of phospho-Ser/Thr-Pro (pS/T-P) motifs in numerous cell-cycle regulatory proteins. These pS/T-P motifs bind to Pin1's peptidyl-prolyl isomerase (PPIase) domain in a catalytic pocket, between an extended catalytic loop and the PPIase domain core. Previous studies showed that post-translational phosphorylation of S71 in the catalytic loop decreases substrate binding affinity and isomerase activity. To define the origins for these effects, we investigated a phosphomimetic Pin1 mutant, S71E-Pin1, using solution NMR. We find that S71E perturbs not only its host loop but also the nearby PPIase core. The perturbations identify a local network of hydrogen bonds and salt bridges that is more extended than previously thought, and includes interactions between the catalytic loop and the α2/α3 turn in the PPIase core. Explicit-solvent molecular dynamics simulations and phylogenetic analysis suggest that these interactions act as conserved "latches" between the loop and PPIase core that enhance binding of phosphorylated substrates, as they are absent in PPIases lacking pS/T-P specificity. Our results suggest that S71 is a hub residue within an electrostatic network primed for phosphorylation, and may illustrate a common mechanism of phosphorylation-mediated allostery. Copyright © 2018 Elsevier Ltd. All rights reserved.

Pressure transients analysis of a high-temperature gas-cooled reactor with direct helium turbine cycle

Energy Technology Data Exchange (ETDEWEB)

Dang, M.; Dupont, J. F.; Jacquemoud, P.; Mylonas, R. [Eidgenoessisches Inst. fuer Reaktorforschung, Wuerenlingen (Switzerland)

1981-01-15

The direct coupling of a gas cooled reactor with a closed gas turbine cycle leads to a specific dynamic plant behaviour, which may be summarized as follows: a) any operational transient involving a variation of the core mass flow rate causes a variation of the pressure ratio of the turbomachines and leads unavoidably to pressure and temperature transients in the gas turbine cycle; and b) very severe pressure equalization transients initiated by unlikely events such as the deblading of one or more turbomachines must be taken into account. This behaviour is described and illustrated through results gained from computer analyses performed at the Swiss Federal Institute for Reactor Research (EIR) in Wurenlingen within the scope of the Swiss-German HHT project.

Direct α-alkylation of ketones with alcohols in water.

Science.gov (United States)

Xu, Guoqiang; Li, Qiong; Feng, Jiange; Liu, Qiang; Zhang, Zuojun; Wang, Xicheng; Zhang, Xiaoyun; Mu, Xindong

2014-01-01

The direct α-alkylation of ketones with alcohols has emerged as a new green protocol to construct C-C bonds with H2 O as the sole byproduct. In this work, a very simple and convenient Pd/C catalytic system for the direct α-alkylation of ketones with primary alcohols in pure water is developed. Based on this catalytic system, aqueous mixtures of dilute acetone, 1-butanol, and ethanol (mimicking ABE fermentation products) can be directly transformed into C5 -C11 or longer-chain ketones and alcohols, which are precursors to fuels. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Crystal structures of wild-type Trichoderma reesei Cel7A catalytic domain in open and closed states

Energy Technology Data Exchange (ETDEWEB)

Bodenheimer, Annette M. [Molecular and Structural Biochemistry Department, North Carolina State University, Raleigh NC USA; Neutron Sciences Directorate, Oak Ridge National Laboratory, TN USA; Meilleur, Flora [Molecular and Structural Biochemistry Department, North Carolina State University, Raleigh NC USA; Neutron Sciences Directorate, Oak Ridge National Laboratory, TN USA

2016-11-07

Trichoderma reesei Cel7A efficiently hydrolyses cellulose. We report here the crystallographic structures of the wild-type TrCel7A catalytic domain (CD) in an open state and, for the first time, in a closed state. Molecular dynamics (MD) simulations indicate that the loops along the CD tunnel move in concerted motions. Together, the crystallographic and MD data suggest that the CD cycles between the tense and relaxed forms that are characteristic of work producing enzymes. Analysis of the interactions formed by R251 provides a structural rationale for the concurrent decrease in product inhibition and catalytic efficiency measured for product-binding site mutants.

A study about the contribution of the α-β phase transition of quartz to thermal cycle damage of a refractory used in fluidized catalytic cracking units

Directory of Open Access Journals (Sweden)

A. H. A. Pereira

2014-09-01

Full Text Available The deterioration of refractories used in fluidized catalytic cracking units (FCC-units is responsible for high costs of maintenance for the petrochemical industry. This is commonly associated with coke deposition during the production of light hydrocarbons. However, other mechanisms responsible for causing damage may also occur, such as the generation of cracks by expansive phase transition. The aim of the work herein was to study the contribution of the a-b phase transition of quartz particles to the deterioration of a commercial aluminosilicate refractory used in a riser by the means of slow thermal cycles. Such damage may occur if the working temperature of the equipment fluctuates around the a-b transition temperature (573 °C. The current study considered the material with and without coke impregnation to evaluate the combined effect of coke presence and phase transition. To evaluate the damage, it was used the Young's modulus as a function of temperature by applying the Impulse Excitation Technique under controlled atmosphere. An equipment recently developed by the authors research group was applied. Specimens were prepared and submitted to slow thermal cycles of temperatures up to 500 °C and up to 700 °C, with a heating rate of 2 °C/min. Part of the specimens was previously impregnated with coke by a reactor using propen. To complete the evaluation, characterization by X-ray diffraction, as well as by dilatometry and scanning electron microscopy were performed. The findings of this study showed that the presence of quartz particles determine the thermo-mechanical behaviour of the material, as well as the thermocycling damage resistance. In spite of the fact that the a-b phase transition stiffens the material during the heating stage, it increases the damage by slow thermal cycling. The coke impregnation increases the resistance to slow thermal cycles, however it decreases the resistance to the damage evolution.

Kinetic and catalytic performance of a BI-porous composite material in catalytic cracking and isomerisation reactions

KAUST Repository

Al-Khattaf, S.

2012-01-10

Catalytic behaviour of pure zeolite ZSM-5 and a bi-porous composite material (BCM) were investigated in transformation of m-xylene, while zeolite HY and the bi-porous composite were used in the cracking of 1,3,5-triisopropylbenzene (TIPB). The micro/mesoporous material was used to understand the effect of the presence of mesopores on these reactions. Various characterisation techniques, that is, XRD, SEM, TGA, FT-IR and nitrogen sorption measurements were applied for complete characterisation of the catalysts. Catalytic tests using CREC riser simulator showed that the micro/mesoporous composite catalyst exhibited higher catalytic activity as compared with the conventional microporous ZSM-5 and HY zeolite for transformation of m-xylene and for the catalytic cracking of TIPB, respectively. The outstanding catalytic reactivity of m-xylene and TIPB molecules were mainly attributed to the easier access of active sites provided by the mesopores. Apparent activation energies for the disappearance of m-xylene and TIPB over all catalysts were found to decrease in the order: EBCM>EZSM-5 and EBCM>EHY, respectively. © 2012 Canadian Society for Chemical Engineering.

Catalytic modification of cellulose and hemicellulose - Sugarefine

Energy Technology Data Exchange (ETDEWEB)

Repo, T. [Helsinki Univ. (Finland),Laboratory of Inorganic Chemistry], email: timo.repo@helsinki.fi

2012-07-01

The main goal of the project is to develop catalytic methods for the modification of lignocellulose-based saccharides in the biorefineries. The products of these reactions could be used for example as biofuel components, raw materials for the chemical industry, solvents and precursors for biopolymers. The catalyst development aims at creating efficient, selective and green catalytic methods for profitable use in biorefineries. The project is divided in three work packages: In WP1 (Catalytic dehydration of cellulose) the aim is at developing non-toxic, efficient methods for the catalytic dehydration of cellulose the target molecule being here 5-hydroxymethylfurfural (5-HMF). 5-HMF is an interesting platform chemical for the production of fuel additives, solvents and polymers. In WP2 (Catalytic reduction), the objective of the catalytic reduction studies is to produce commercially interesting monofunctional chemicals, such as 1-butanol or 2-methyltetrahydrofuran (2-MeTHF). In WP3 (Catalytic oxidation), the research focuses on developing a green and efficient oxidation method for producing acids. Whereas acetic and formic acids are bulk chemicals, diacids such as glucaric and xylaric acids are valuable specialty chemicals for detergent, polymer and food production.

Direct decarbonylation of furfural to furan: A density functional theory study on Pt-graphene

Science.gov (United States)

Fellah, Mehmet Ferdi

2017-05-01

The catalytic mechanism of direct decarbonylation of furfural to furan on Pt graphene surface has been investigated by means of density functional theory (DFT) calculations. The main catalytic mechanism proposed in this study has six steps such as furfural adsorption, dissociation of H from adsorbed furfural, dissociation of carbon monoxide (molecularly) from adsorbed complex, furan formation and desorption of products. It has been concluded that the rate determining step for direct decarbonylation of furfural to furan is furan formation step and global activation barrier for this catalytic system is 82 kJ/mol consisting of zero point energy and thermal energy corrections. Pt-graphene structure has an important role on the catalytic decarbonylation of furfural to furan without any other reactants. This accordingly points out that Pt doped graphene structure might be an encouraging catalyst for direct decarbonylation of furfural to furan molecule as a valuable chemical material.

Cytochromes P450: History, Classes, Catalytic Mechanism, and Industrial Application.

Science.gov (United States)

Cook, D J; Finnigan, J D; Cook, K; Black, G W; Charnock, S J

Cytochromes P450, a family of heme-containing monooxygenases that catalyze a diverse range of oxidative reactions, are so-called due to their maximum absorbance at 450nm, ie, "Pigment-450nm," when bound to carbon monoxide. They have appeal both academically and commercially due to their high degree of regio- and stereoselectivity, for example, in the area of active pharmaceutical ingredient synthesis. Despite this potential, they often exhibit poor stability, low turnover numbers and typically require electron transport protein(s) for catalysis. P450 systems exist in a variety of functional domain architectures, organized into 10 classes. P450s are also divided into families, each of which is based solely on amino acid sequence homology. Their catalytic mechanism employs a very complex, multistep catalytic cycle involving a range of transient intermediates. Mutagenesis is a powerful tool for the development of improved biocatalysts and has been used extensively with the archetypal Class VIII P450, BM3, from Bacillus megaterium, but with the increasing scale of genomic sequencing, a huge resource is now available for the discovery of novel P450s. © 2016 Elsevier Inc. All rights reserved.

Reaction Current Phenomenon in Bifunctional Catalytic Metal-Semiconductor Nanostructures

Science.gov (United States)

Hashemian, Mohammad Amin

Energy transfer processes accompany every elementary step of catalytic chemical processes on material surface including molecular adsorption and dissociation on atoms, interactions between intermediates, and desorption of reaction products from the catalyst surface. Therefore, detailed understanding of these processes on the molecular level is of great fundamental and practical interest in energy-related applications of nanomaterials. Two main mechanisms of energy transfer from adsorbed particles to a surface are known: (i) adiabatic via excitation of quantized lattice vibrations (phonons) and (ii) non-adiabatic via electronic excitations (electron/hole pairs). Electronic excitations play a key role in nanocatalysis, and it was recently shown that they can be efficiently detected and studied using Schottky-type catalytic nanostructures in the form of measureable electrical currents (chemicurrents) in an external electrical circuit. These nanostructures typically contain an electrically continuous nanocathode layers made of a catalytic metal deposited on a semiconductor substrate. The goal of this research is to study the direct observations of hot electron currents (chemicurrents) in catalytic Schottky structures, using a continuous mesh-like Pt nanofilm grown onto a mesoporous TiO2 substrate. Such devices showed qualitatively different and more diverse signal properties, compared to the earlier devices using smooth substrates, which could only be explained on the basis of bifunctionality. In particular, it was necessary to suggest that different stages of the reaction are occurring on both phases of the catalytic structure. Analysis of the signal behavior also led to discovery of a formerly unknown (very slow) mode of the oxyhydrogen reaction on the Pt/TiO2(por) system occurring at room temperature. This slow mode was producing surprisingly large stationary chemicurrents in the range 10--50 microA/cm2. Results of the chemicurrent measurements for the bifunctional

Engineering reactors for catalytic reactions

Indian Academy of Sciences (India)

Extensive studies have been conducted to establish sound basis for design and engineering of reactors for practising such catalytic reactions and for realizing improvements in reactor performance. In this article, application of recent (and not so recent) developments in engineering reactors for catalytic reactions is ...

Mechanistic evidence for a ring-opening pathway in the Pd-catalyzed direct arylation of benzoxazoles

DEFF Research Database (Denmark)

Sanchez, R.S.; Zhuravlev, Fedor

2007-01-01

The direct Pd-catalyzed arylation of 5-substituted benzoxazoles, used as a mechanistic model for 1,3-azoles, was investigated experimentally and computationally. The results of the primary deuterium kinetic isotope effect, Hammett studies, and H/D exchange were shown to be inconsistent with the r......The direct Pd-catalyzed arylation of 5-substituted benzoxazoles, used as a mechanistic model for 1,3-azoles, was investigated experimentally and computationally. The results of the primary deuterium kinetic isotope effect, Hammett studies, and H/D exchange were shown to be inconsistent...... with the rate-limiting electrophilic or concerted palladation. A mechanism, proposed on the basis of kinetic and computational studies, includes generation of isocyanophenolate as the key step. The DFT calculations suggest that the overall catalytic cycle is facile and is largely controlled by the C-H acidity...

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

Energy Technology Data Exchange (ETDEWEB)

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

2017-04-18

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

Evaluation of technical feasibility of closed-cycle non-equilibrium MHD power generation with direct coal firing. Final report, Task I

Energy Technology Data Exchange (ETDEWEB)

1981-11-01

Program accomplishments in a continuing effort to demonstrate the feasibility of direct coal-fired, closed-cycle MHD power generation are reported. This volume contains the following appendices: (A) user's manual for 2-dimensional MHD generator code (2DEM); (B) performance estimates for a nominal 30 MW argon segmented heater; (C) the feedwater cooled Brayton cycle; (D) application of CCMHD in an industrial cogeneration environment; (E) preliminary design for shell and tube primary heat exchanger; and (F) plant efficiency as a function of output power for open and closed cycle MHD power plants. (WHK)

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

Energy Technology Data Exchange (ETDEWEB)

Czernik, S.; Wang, D.; Chornet, E. [National Renewable Energy Lab., Golden, CO (United States). Center for Renewable Chemical Technologies and Materials

1998-08-01

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

Plant characteristics of an integrated solid oxide fuel cell cycle and a steam cycle

International Nuclear Information System (INIS)

Rokni, Masoud

2010-01-01

Plant characteristics of a system containing a solid oxide fuel cell (SOFC) cycle on the top of a Rankine cycle were investigated. A desulfurization reactor removes the sulfur content in the fuel, while a pre-reformer broke down the heavier hydrocarbons in an adiabatic steam reformer (ASR). The pre-treated fuel then entered to the anode side of the SOFC. The remaining fuels after the SOFC stacks entered a catalytic burner for further combusting. The burned gases from the burner were then used to produce steam for the Rankine cycle in a heat recovery steam generator (HRSG). The remaining energy of the off-gases was recycled back to the topping cycle for further utilization. Several parameter studies were carried out to investigate the sensitivity of the suggested plant. It was shown that the operation temperature of the desulfurization and the pre-reformer had no effect on the plant efficiency, which was also true when decreasing the anode temperature. However, increasing the cathode temperature had a significant effect on the plant efficiency. In addition, decreasing the SOFC utilization factor from 0.8 to 0.7, increases the plant efficiency by about 6%. An optimal plant efficiency of about 71% was achieved by optimizing the plant.

Plant characteristics of an integrated solid oxide fuel cell cycle and a steam cycle

Energy Technology Data Exchange (ETDEWEB)

Rokni, Masoud [Technical University of Denmark, Dept. of Mechanical Engineering, Thermal Energy System, Building 402, 2800 Kgs, Lyngby (Denmark)

2010-12-15

Plant characteristics of a system containing a solid oxide fuel cell (SOFC) cycle on the top of a Rankine cycle were investigated. A desulfurization reactor removes the sulfur content in the fuel, while a pre-reformer broke down the heavier hydrocarbons in an adiabatic steam reformer (ASR). The pre-treated fuel then entered to the anode side of the SOFC. The remaining fuels after the SOFC stacks entered a catalytic burner for further combusting. The burned gases from the burner were then used to produce steam for the Rankine cycle in a heat recovery steam generator (HRSG). The remaining energy of the off-gases was recycled back to the topping cycle for further utilization. Several parameter studies were carried out to investigate the sensitivity of the suggested plant. It was shown that the operation temperature of the desulfurization and the pre-reformer had no effect on the plant efficiency, which was also true when decreasing the anode temperature. However, increasing the cathode temperature had a significant effect on the plant efficiency. In addition, decreasing the SOFC utilization factor from 0.8 to 0.7, increases the plant efficiency by about 6%. An optimal plant efficiency of about 71% was achieved by optimizing the plant. (author)

Optimisation of a Kalina cycle for a central receiver solar thermal power plant with direct steam generation

DEFF Research Database (Denmark)

Modi, Anish; Haglind, Fredrik

2014-01-01

Central receiver solar thermal power plants are regarded as one of the promising ways to generate electricity in near future. They offer the possibility of using high temperatures and pressures to achieve high efficiencies with standard power cycles. A direct steam generation approach can be used...

Metal–Organic Frameworks Stabilize Mono(phosphine)–Metal Complexes for Broad-Scope Catalytic Reactions

Energy Technology Data Exchange (ETDEWEB)

Sawano, Takahiro; Lin, Zekai; Boures, Dean; An, Bing; Wang, Cheng; Lin, Wenbin (UC); (Xiamen)

2016-08-10

Mono(phosphine)–M (M–PR3; M = Rh and Ir) complexes selectively prepared by postsynthetic metalation of a porous triarylphosphine-based metal–organic framework (MOF) exhibited excellent activity in the hydrosilylation of ketones and alkenes, the hydrogenation of alkenes, and the C–H borylation of arenes. The recyclable and reusable MOF catalysts significantly outperformed their homogeneous counterparts, presumably via stabilizing M–PR3 intermediates by preventing deleterious disproportionation reactions/ligand exchanges in the catalytic cycles.

Trends in catalytic NO decomposition over transition metal surfaces

DEFF Research Database (Denmark)

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

2007-01-01

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

Catalytic steam reforming of tar derived from steam gasification of sunflower stalk over ethylene glycol assisting prepared Ni/MCM-41

International Nuclear Information System (INIS)

Karnjanakom, Surachai; Guan, Guoqing; Asep, Bayu; Du, Xiao; Hao, Xiaogang; Samart, Chanatip; Abudula, Abuliti

2015-01-01

Highlights: • Ni/MCM-41 was prepared by EG-assisted co-impregnation method. • EG-assisted co-impregnation method resulted in Ni particles well dispersed on MCM-41. • Ni/MCM-41-EG catalyst had high catalytic activity for tar reforming. • The highest H 2 gas yield was obtained when using 20 wt.% Ni/MCM-41-EG. • The catalysts were reused up to 5 cycles without any serious deactivation. - Abstract: Ethylene glycol (EG) assisted impregnation of nickel catalyst on MCM-41 (Ni/MCM-41-EG) was performed and applied for steam reforming of tar derived from biomass. The catalyst was characterized by SEM–EDX, BET, XRD, and TPR. It is found that smaller nickel particles were well dispersed on MCM-41 and better catalytic activity was shown for the Ni/MCM-41-EG when compared with the catalyst of Ni/MCM-41 prepared by using the conventional impregnation method. H 2 yield increased approximately 8% when using 20 wt.% Ni/MCM-41-EG instead of 20 wt.% Ni/MCM-41 for the steam reforming of tar derived from sunflower stalk. The catalyst reusability was also tested up to five cycles, and no obvious activity reduction was observed. It indicates that EG assisted impregnation method is a good way to prepare metal loaded porous catalyst with high catalytic activity, high loading amount and long-term stability for the tar reforming

Cell Cycle Regulates Nuclear Stability of AID and Determines the Cellular Response to AID.

Directory of Open Access Journals (Sweden)

Quy Le

2015-09-01

Full Text Available AID (Activation Induced Deaminase deaminates cytosines in DNA to initiate immunoglobulin gene diversification and to reprogram CpG methylation in early development. AID is potentially highly mutagenic, and it causes genomic instability evident as translocations in B cell malignancies. Here we show that AID is cell cycle regulated. By high content screening microscopy, we demonstrate that AID undergoes nuclear degradation more slowly in G1 phase than in S or G2-M phase, and that mutations that affect regulatory phosphorylation or catalytic activity can alter AID stability and abundance. We directly test the role of cell cycle regulation by fusing AID to tags that destabilize nuclear protein outside of G1 or S-G2/M phases. We show that enforced nuclear localization of AID in G1 phase accelerates somatic hypermutation and class switch recombination, and is well-tolerated; while nuclear AID compromises viability in S-G2/M phase cells. We identify AID derivatives that accelerate somatic hypermutation with minimal impact on viability, which will be useful tools for engineering genes and proteins by iterative mutagenesis and selection. Our results further suggest that use of cell cycle tags to regulate nuclear stability may be generally applicable to studying DNA repair and to engineering the genome.

Heterogeneous Photo catalytic Degradation of Hazardous Waste in Aqueous Suspension

International Nuclear Information System (INIS)

Sadek, S.A.; Ebraheem, S.; Friesen, K.J.

1999-01-01

The photo catalytic degradation of hazardous waste like chlorinated paraffin compound (1,12-Dichlorodoecane Ded) was investigated in different aquatic media using GC-MSD. The direct photolysis of Ded in HPLC water was considered to be negligible (k = 0.0020+-0.0007h - 1 ) . An acceleration of the photodegradation rate was occurred in presence of different TiO 2 catalyst systems. Molecular oxygen was found to play a vital role in the degradation process. Anatase TiO 2 was proved to be the most efficient one (k=0.7670+-0.0876h -1 ), while the rate constant of the rutile TiO 2 was calculated to be 0.2780+-0.0342h -1 . Improvement of photo catalytic efficiency of rutile TiO 2 was achieved by addition of Fe +2 giving a rate constant =0.6710+-0.0786h -1

Ultraviolet laser deposition of graphene thin films without catalytic layers

KAUST Repository

Sarath Kumar, S. R.; Alshareef, Husam N.

2013-01-01

In this letter, the formation of nanostructured graphene by ultraviolet laser ablation of a highly ordered pyrolytic graphite target under optimized conditions is demonstrated, without a catalytic layer, and a model for the growth process is proposed. Previously, graphene film deposition by low-energy laser (2.3 eV) was explained by photo-thermal models, which implied that graphene films cannot be deposited by laser energies higher than the C-C bond energy in highly ordered pyrolytic graphite (3.7 eV). Here, we show that nanostructured graphene films can in fact be deposited using ultraviolet laser (5 eV) directly over different substrates, without a catalytic layer. The formation of graphene is explained by bond-breaking assisted by photoelectronic excitation leading to formation of carbon clusters at the target and annealing out of defects at the substrate.

Ultraviolet laser deposition of graphene thin films without catalytic layers

KAUST Repository

Sarath Kumar, S. R.

2013-01-09

In this letter, the formation of nanostructured graphene by ultraviolet laser ablation of a highly ordered pyrolytic graphite target under optimized conditions is demonstrated, without a catalytic layer, and a model for the growth process is proposed. Previously, graphene film deposition by low-energy laser (2.3 eV) was explained by photo-thermal models, which implied that graphene films cannot be deposited by laser energies higher than the C-C bond energy in highly ordered pyrolytic graphite (3.7 eV). Here, we show that nanostructured graphene films can in fact be deposited using ultraviolet laser (5 eV) directly over different substrates, without a catalytic layer. The formation of graphene is explained by bond-breaking assisted by photoelectronic excitation leading to formation of carbon clusters at the target and annealing out of defects at the substrate.

Reactivating Catalytic Surface: Insights into the Role of Hot Holes in Plasmonic Catalysis.

Science.gov (United States)

Peng, Tianhuan; Miao, Junjian; Gao, Zhaoshuai; Zhang, Linjuan; Gao, Yi; Fan, Chunhai; Li, Di

2018-03-01

Surface plasmon resonance of coinage metal nanoparticles is extensively exploited to promote catalytic reactions via harvesting solar energy. Previous efforts on elucidating the mechanisms of enhanced catalysis are devoted to hot electron-induced photothermal conversion and direct charge transfer to the adsorbed reactants. However, little attention is paid to roles of hot holes that are generated concomitantly with hot electrons. In this work, 13 nm spherical Au nanoparticles with small absorption cross-section are employed to catalyze a well-studied glucose oxidation reaction. Density functional theory calculation and X-ray absorption spectrum analysis reveal that hot holes energetically favor transferring catalytic intermediates to product molecules and then desorbing from the surface of plasmonic catalysts, resulting in the recovery of their catalytic activities. The studies shed new light on the use of the synergy of hot holes and hot electrons for plasmon-promoted catalysis. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fabrication of Core-Shell Structural SiO2@H3[PM12O40] Material and Its Catalytic Activity

Directory of Open Access Journals (Sweden)

Xin Yang

2014-01-01

Full Text Available Through a natural tree grain template and sol-gel technology, the heterogeneous catalytic materials based on polyoxometalate compounds H3[PM12O40] encapsulating SiO2: SiO2@H3[PM12O40] (SiO2@PM12, M = W, Mo with core-shell structure had been prepared. The structure and morphology of the core-shell microspheres were characterized by the XRD, IR spectroscopy, UV-Vis absorbance, and SEM. These microsphere materials can be used as heterogeneous catalysts with high activity and stability for catalytic wet air oxidation of pollutant dyes safranine T (ST at room condition. The results show that the catalysts have excellent catalytic activity in treatment of wastewater containing 10 mg/L ST, and 94% of color can be removed within 60 min. Under different cycling runs, it is shown that the catalysts are stable under such operating conditions and the leaching tests show negligible leaching effect owing to the lesser dissolution.

Understanding Catalytic Activity Trends for NO Decomposition and CO Oxidation using Density Functional Theory and Microkinetic Modeling

DEFF Research Database (Denmark)

Falsig, Hanne

-metal surfaces by combining a database of adsorption energies on stepped metal surfaces with known Brønsted–Evans–Polanyi (BEP) relations for the activation barriers of dissociation of diatomic molecules over stepped transition- and noble-metal surfaces. The potential energy diagram directly points to why Pd......The main aim of this thesis is to understand the catalytic activity of transition metals and noble metals for the direct decomposition of NO and the oxidation of CO. The formation of NOx from combustion of fossil and renewable fuels continues to be a dominant environmental issue. We take one step...... towards rationalizing trends in catalytic activity of transition metal catalysts for NO decomposition by combining microkinetic modelling with density functional theory calculations. We establish the full potential energy diagram for the direct NO decomposition reaction over stepped transition...

Direct catalytic olefination of alcohols with sulfones.

Science.gov (United States)

Srimani, Dipankar; Leitus, Gregory; Ben-David, Yehoshoa; Milstein, David

2014-10-06

The synthesis of terminal, as well as internal, olefins was achieved by the one-step olefination of alcohols with sulfones catalyzed by a ruthenium pincer complex. Furthermore, performing the reaction with dimethyl sulfone under mild hydrogen pressure provides a direct route for the replacement of alcohol hydroxy groups by methyl groups in one step. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis, spectroscopic characterization and catalytic oxidation ...

Indian Academy of Sciences (India)

were characterized by infrared, electronic, electron paramagnetic resonance ... The catalytic oxidation property of ruthenium(III) complexes were also ... cies at room temperature. ..... aldehyde part of Schiff base ligands, catalytic activ- ity of new ...

Automatic cardiac cycle determination directly from EEG-fMRI data by multi-scale peak detection method.

Science.gov (United States)

Wong, Chung-Ki; Luo, Qingfei; Zotev, Vadim; Phillips, Raquel; Chan, Kam Wai Clifford; Bodurka, Jerzy

2018-03-31

In simultaneous EEG-fMRI, identification of the period of cardioballistic artifact (BCG) in EEG is required for the artifact removal. Recording the electrocardiogram (ECG) waveform during fMRI is difficult, often causing inaccurate period detection. Since the waveform of the BCG extracted by independent component analysis (ICA) is relatively invariable compared to the ECG waveform, we propose a multiple-scale peak-detection algorithm to determine the BCG cycle directly from the EEG data. The algorithm first extracts the high contrast BCG component from the EEG data by ICA. The BCG cycle is then estimated by band-pass filtering the component around the fundamental frequency identified from its energy spectral density, and the peak of BCG artifact occurrence is selected from each of the estimated cycle. The algorithm is shown to achieve a high accuracy on a large EEG-fMRI dataset. It is also adaptive to various heart rates without the needs of adjusting the threshold parameters. The cycle detection remains accurate with the scan duration reduced to half a minute. Additionally, the algorithm gives a figure of merit to evaluate the reliability of the detection accuracy. The algorithm is shown to give a higher detection accuracy than the commonly used cycle detection algorithm fmrib_qrsdetect implemented in EEGLAB. The achieved high cycle detection accuracy of our algorithm without using the ECG waveforms makes possible to create and automate pipelines for processing large EEG-fMRI datasets, and virtually eliminates the need for ECG recordings for BCG artifact removal. Copyright © 2018 The Authors. Published by Elsevier B.V. All rights reserved.

Catalytic exhaust control

Energy Technology Data Exchange (ETDEWEB)

Heinemann, H

1973-09-01

Recent achievements and problems in the development of exhaust control devices in the USA are reviewed. To meet the 1976 emission standards, catalytic systems for the oxidation of carbon monoxide and hydrocarbons and for the reduction of nitrogen oxides to nitrogen and water are needed. While oxidizing catalysts using platinum, palladium, copper, vanadium, and chromium appplied on alumina or ceramic materials are more or less effective in emission control, there are no catalytic devices for the reduction of nitrogen oxides with the required useful life of 25,000 to 50,000 miles as yet available. In the case of platinum catalysts on monolithic supports, the operating temperature of 650 to 750/sup 0/C as required for the oxidation process may cause inactivation of the catalysts and fusion of the support material. The oxidation of CO and hydrocarbons is inhibited by high concentrations of CO, nitric oxide, and hydrocarbons. The use of catalytic converters requires the use of lead-free or low-lead gasoline. The nitrogen oxides conversion efficiency is considerably influenced by the oxygen-to-CO ratio of the exhaust gas, which makes limitation of this ratio necessary.

New URJC-1 Material with Remarkable Stability and Acid-Base Catalytic Properties

Directory of Open Access Journals (Sweden)

Pedro Leo

2016-02-01

Full Text Available Emerging new metal-organic structures with tunable physicochemical properties is an exciting research field for diverse applications. In this work, a novel metal-organic framework Cu(HIT(DMF0.5, named URJC-1, with a three-dimensional non-interpenetrated utp topological network, has been synthesized. This material exhibits a microporous structure with unsaturated copper centers and imidazole–tetrazole linkages that provide accessible Lewis acid/base sites. These features make URJC-1 an exceptional candidate for catalytic application in acid and base reactions of interest in fine chemistry. The URJC-1 material also displays a noteworthy thermal and chemical stability in different organic solvents of different polarity and boiling water. Its catalytic activity was evaluated in acid-catalyzed Friedel–Crafts acylation of anisole with acetyl chloride and base-catalyzed Knoevenagel condensation of benzaldehyde with malononitrile. In both cases, URJC-1 material showed very good performance, better than other metal organic frameworks and conventional catalysts. In addition, a remarkable structural stability was proven after several consecutive reaction cycles.

Preparation of silver nanoparticles/polydopamine functionalized polyacrylonitrile fiber paper and its catalytic activity for the reduction 4-nitrophenol

Energy Technology Data Exchange (ETDEWEB)

Lu, Shixiang, E-mail: shixianglu@bit.edu.cn [School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081 (China); Univ. Lille, CNRS, Centrale Lille, ISEN, Univ. Valenciennes, UMR 8520 – IEMN, Lille F-59000 (France); Yu, Jianying; Cheng, Yuanyuan [School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081 (China); Wang, Qian; Barras, Alexandre [Univ. Lille, CNRS, Centrale Lille, ISEN, Univ. Valenciennes, UMR 8520 – IEMN, Lille F-59000 (France); Xu, Wenguo [School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081 (China); Szunerits, Sabine [Univ. Lille, CNRS, Centrale Lille, ISEN, Univ. Valenciennes, UMR 8520 – IEMN, Lille F-59000 (France); Cornu, David [Institut Européen des Membranes, UMR 5635, Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), CNRS, Université Montpellier 2, 276 rue de la Galéra, Montpellier 34000 (France); Boukherroub, Rabah, E-mail: rabah.boukherroub@iemn.univ-lille1.fr [Univ. Lille, CNRS, Centrale Lille, ISEN, Univ. Valenciennes, UMR 8520 – IEMN, Lille F-59000 (France)

2017-07-31

Graphical abstract: Illustration of the preparation of Ag nanoparticles coated paper and its catalytic application for 4-nitrophenol reduction into the corresponding 4-aminophenol. - Highlights: • Polyacrylonitrile paper was functionalized with polydopamine and Ag nanoparticles. • Polydopamine coating layer played both reductive and adhesive roles. • The composite material displayed good catalytic activity for 4-nitrophenol reduction. • The process was environmentally benign and facile. - Abstract: The study reports on the preparation of polyacrylonitrile fiber paper (PANFP) functionalized with polydopamine (PD) and silver nanoparticles (Ag NPs), named as Ag NPs/PD/PANFP. The composite material was obtained via a simple two-step chemical process. First, a thin polydopamine layer was coated onto the PANFP surface through immersion into an alkaline dopamine (pH 8.5) aqueous solution at room temperature. The reductive properties of polydopamine were further exploited for the deposition of Ag NPs. The morphology and chemical composition of the composite material were characterized using scanning electron microscopy (SEM), X-ray diffraction pattern (XRD) and X-ray photoelectron spectroscopy (XPS). The catalytic activity of the nanocomposite was evaluated for the reduction of 4-nitrophenol using sodium borohydride (NaBH{sub 4}) at room temperature. The Ag NPs/PD/PANFP displayed good catalytic performance with a full reduction of 4-nitrophenol into the corresponding 4-aminophenol within 30 min. Moreover, the composite material exhibited a good stability up to 4 cycles without a significant loss of its catalytic activity.

Catalytic Wittig and aza-Wittig reactions

Directory of Open Access Journals (Sweden)

Zhiqi Lao

2016-11-01

Full Text Available This review surveys the literature regarding the development of catalytic versions of the Wittig and aza-Wittig reactions. The first section summarizes how arsenic and tellurium-based catalytic Wittig-type reaction systems were developed first due to the relatively easy reduction of the oxides involved. This is followed by a presentation of the current state of the art regarding phosphine-catalyzed Wittig reactions. The second section covers the field of related catalytic aza-Wittig reactions that are catalyzed by both phosphine oxides and phosphines.

Efficient catalytic combustion in integrated micropellistors

International Nuclear Information System (INIS)

Bársony, I; Ádám, M; Fürjes, P; Dücső, Cs; Lucklum, R; Hirschfelder, M; Kulinyi, S

2009-01-01

This paper analyses two of the key issues of the development of catalytic combustion-type sensors: the selection and production of active catalytic particles on the micropellistor surface as well as the realization of a reliable thermal conduction between heater element and catalytic surface, for the sensing of temperature increase produced by the combustion. The report also demonstrates that chemical sensor product development by a MEMS process is a continuous struggle for elimination of all uncertainties influencing reliability and sensitivity of the final product

Adsorbent catalytic nanoparticles and methods of using the same

Energy Technology Data Exchange (ETDEWEB)

Slowing, Igor Ivan; Kandel, Kapil

2017-01-31

The present invention provides an adsorbent catalytic nanoparticle including a mesoporous silica nanoparticle having at least one adsorbent functional group bound thereto. The adsorbent catalytic nanoparticle also includes at least one catalytic material. In various embodiments, the present invention provides methods of using and making the adsorbent catalytic nanoparticles. In some examples, the adsorbent catalytic nanoparticles can be used to selectively remove fatty acids from feedstocks for biodiesel, and to hydrotreat the separated fatty acids.

Water oxidation catalyzed by mononuclear ruthenium complexes with a 2,2'-bipyridine-6,6'-dicarboxylate (bda) ligand: how ligand environment influences the catalytic behavior.

Science.gov (United States)

Staehle, Robert; Tong, Lianpeng; Wang, Lei; Duan, Lele; Fischer, Andreas; Ahlquist, Mårten S G; Sun, Licheng; Rau, Sven

2014-02-03

A new water oxidation catalyst [Ru(III)(bda)(mmi)(OH2)](CF3SO3) (2, H2bda = 2,2'-bipyridine-6,6'-dicarboxylic acid; mmi = 1,3-dimethylimidazolium-2-ylidene) containing an axial N-heterocyclic carbene ligand and one aqua ligand was synthesized and fully characterized. The kinetics of catalytic water oxidation by 2 were measured using stopped-flow technique, and key intermediates in the catalytic cycle were probed by density functional theory calculations. While analogous Ru-bda water oxidation catalysts [Ru(bda)L2] (L = pyridyl ligands) are supposed to catalyze water oxidation through a bimolecular coupling pathway, our study points out that 2, surprisingly, undergoes a single-site water nucleophilic attack (acid-base) pathway. The diversion of catalytic mechanisms is mainly ascribed to the different ligand environments, from nonaqua ligands to an aqua ligand. Findings in this work provide some critical proof for our previous hypothesis about how alternation of ancillary ligands of water oxidation catalysts influences their catalytic efficiency.

Catalytic pyrolysis of hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Vail' eva, N A; Buyanov, R A

1979-01-01

Catalytic pyrolysis of petroleum fractions (undecane) was performed with the object of clarifying such questions as the mechanism of action of the catalyst, the concepts of activity and selectivity of the catalyst, the role of transport processes, the temperature ranges and limitations of the catalytic process, the effect of the catalyst on secondary processes, and others. Catalysts such as quartz, MgO, Al/sub 2/O/sub 3/, were used. Analysis of the experimental findings and the fact that the distribution of products is independent of the nature of the surface, demonstrate that the pyrolysis of hydrocarbons in the presence of catalysts is based on the heterogeneous-homogeneous radical-chain mechanism of action, and that the role of the catalysts reduces to increasing the concentration of free radicals. The concept of selectivity cannot be applied to catalysts here, since they do not affect the mechanism of the unfolding of the process of pyrolysis and their role consists solely in initiating the process. In catalytic pyrolysis the concepts of kinetic and diffusive domains of unfolding of the catalytic reaction do not apply, and only the outer surface of the catalyst is engaged, whereas the inner surface merely promotes deletorious secondary processes reducing the selectivity of the process and the activity of the catalyst. 6 references, 2 figures.

Facile Fabrication of Highly Active Magnetic Aminoclay Supported Palladium Nanoparticles for the Room Temperature Catalytic Reduction of Nitrophenol and Nitroanilines

Directory of Open Access Journals (Sweden)

Lei Jia

2018-06-01

Full Text Available Magnetically recyclable nanocatalysts with excellent performance are urgent need in heterogeneous catalysis, due to their magnetic nature, which allows for convenient and efficient separation with the help of an external magnetic field. In this research, we developed a simple and rapid method to fabricate a magnetic aminoclay (AC based an AC@Fe3O4@Pd nanocatalyst by depositing palladium nanoparticles (Pd NPs on the surface of the magnetic aminoclay nanocomposite. The microstructure and the magnetic properties of as-prepared AC@Fe3O4@Pd were tested using transmission electron microscopy (TEM, energy-dispersive X-ray spectroscopy (EDS, X-ray diffraction (XRD, and vibrating sample magnetometry (VSM analyses. The resultant AC@Fe3O4@Pd nanocatalyst with the magnetic Fe-based inner shell, catalytically activate the outer noble metal shell, which when combined with ultrafine Pd NPs, synergistically enhanced the catalytic activity and recyclability in organocatalysis. As the aminoclay displayed good water dispersibility, the nanocatalyst indicated satisfactory catalytic performance in the reaction of reducing nitrophenol and nitroanilines to the corresponding aminobenzene derivatives. Meanwhile, the AC@Fe3O4@Pd nanocatalyst exhibited excellent reusability, while still maintaining good activity after several catalytic cycles.

Catalytic cracking models developed for predictive control purposes

Directory of Open Access Journals (Sweden)

Dag Ljungqvist

1993-04-01

Full Text Available The paper deals with state-space modeling issues in the context of model-predictive control, with application to catalytic cracking. Emphasis is placed on model establishment, verification and online adjustment. Both the Fluid Catalytic Cracking (FCC and the Residual Catalytic Cracking (RCC units are discussed. Catalytic cracking units involve complex interactive processes which are difficult to operate and control in an economically optimal way. The strong nonlinearities of the FCC process mean that the control calculation should be based on a nonlinear model with the relevant constraints included. However, the model can be simple compared to the complexity of the catalytic cracking plant. Model validity is ensured by a robust online model adjustment strategy. Model-predictive control schemes based on linear convolution models have been successfully applied to the supervisory dynamic control of catalytic cracking units, and the control can be further improved by the SSPC scheme.

Effect of inlet cone pipe angle in catalytic converter

Science.gov (United States)

Amira Zainal, Nurul; Farhain Azmi, Ezzatul; Arifin Samad, Mohd

2018-03-01

The catalytic converter shows significant consequence to improve the performance of the vehicle start from it launched into production. Nowadays, the geometric design of the catalytic converter has become critical to avoid the behavior of backpressure in the exhaust system. The backpressure essentially reduced the performance of vehicles and increased the fuel consumption gradually. Consequently, this study aims to design various models of catalytic converter and optimize the volume of fluid flow inside the catalytic converter by changing the inlet cone pipe angles. Three different geometry angles of the inlet cone pipe of the catalytic converter were assessed. The model is simulated in Solidworks software to determine the optimum geometric design of the catalytic converter. The result showed that by decreasing the divergence angle of inlet cone pipe will upsurge the performance of the catalytic converter.

Catalytic monolayer voltammetry and in situ scanning tunneling microscopy of copper nitrite reductase on cysteamine-modified Au(111) electrodes

DEFF Research Database (Denmark)

Zhang, Jingdong; Welinder, A.C.; Hansen, Allan Glargaard

2003-01-01

electrochemical scanning tunneling microscopy (in situ STM) directly in aqueous acetate buffer, pH 6.0 has been used. High-resolution in situ STM shows that cysteamine packs into ordered domains with strip features of a periodic distance of 11.7 +/- 0.3 Angstrom. No voltammetric signals of the nitrite substrate...... on this surface could be detected. A strong cathodic catalytic wave appears in the presence of nitrite. The catalytic current follows a Michaelis-Menten pattern with a Michaelis constant of K-m approximate to 44 muM, which is close to the value for AxCuNiR in homogeneous solution. The apparent catalytic rate...

ADVANCED BYPRODUCT RECOVERY: DIRECT CATALYTIC REDUCTION OF SO2 TO ELEMENTAL SULFUR; FINAL

International Nuclear Information System (INIS)

Robert S. Weber

1999-01-01

Arthur D. Little, Inc., together with its commercialization partner, Engelhard Corporation, and its university partner Tufts, investigated a single-step process for direct, catalytic reduction of sulfur dioxide from regenerable flue gas desulfurization processes to the more valuable elemental sulfur by-product. This development built on recently demonstrated SO(sub 2)-reduction catalyst performance at Tufts University on a DOE-sponsored program and is, in principle, applicable to processing of regenerator off-gases from all regenerable SO(sub 2)-control processes. In this program, laboratory-scale catalyst optimization work at Tufts was combined with supported catalyst formulation work at Engelhard, bench-scale supported catalyst testing at Arthur D. Little and market assessments, also by Arthur D. Little. Objectives included identification and performance evaluation of a catalyst which is robust and flexible with regard to choice of reducing gas. The catalyst formulation was improved significantly over the course of this work owing to the identification of a number of underlying phenomena that tended to reduce catalyst selectivity. The most promising catalysts discovered in the bench-scale tests at Tufts were transformed into monolith-supported catalysts at Engelhard. These catalyst samples were tested at larger scale at Arthur D. Little, where the laboratory-scale results were confirmed, namely that the catalysts do effectively reduce sulfur dioxide to elemental sulfur when operated under appropriate levels of conversion and in conditions that do not contain too much water or hydrogen. Ways to overcome those limitations were suggested by the laboratory results. Nonetheless, at the end of Phase I, the catalysts did not exhibit the very stringent levels of activity or selectivity that would have permitted ready scale-up to pilot or commercial operation. Therefore, we chose not to pursue Phase II of this work which would have included further bench-scale testing

Catalytic Enantioselective Alkylation of β-Keto Esters with Xanthydrol in the Presence of Chiral Palladium Complex

Energy Technology Data Exchange (ETDEWEB)

Kim, Kyu Yeon; Kim, Dae Young [Soonchunhyang Univ., Asan (Korea, Republic of)

2016-01-15

Our research interest has been directed toward the development of synthetic methods for the enantioselective construction of stereogenic carbon centers. Recently, we explored the catalytic enantioselective functionalization of active methines in the presence of chiral palladium(II) complexes. In conclusion, we have accomplished the efficient catalytic enantioselective alkylation of β-keto esters 1 with xanthydrol 2 with high yields and excellent enantioselectivity (up to 98% ee). It should be noted that this alkyaltion reaction proceeds well using air- and moisture-stable chiral palladium com- plexes with low loading (1 mol%)

Catalytic burners in larger boiler appliances

Energy Technology Data Exchange (ETDEWEB)

Silversand, Fredrik; Persson, Mikael (Catator AB, Lund (Sweden))

2009-02-15

This project focuses on the scale up of a Catator's catalytic burner technology to enable retrofit installation in existing boilers and the design of new innovative combinations of catalytic burners and boilers. Different design approaches are discussed and evaluated in the report and suggestions are made concerning scale-up. Preliminary test data, extracted from a large boiler installation are discussed together with an accurate analysis of technical possibilities following an optimization of the boiler design to benefit from the advantages of catalytic combustion. The experimental work was conducted in close collaboration with ICI Caldaie (ICI), located in Verona, Italy. ICI is a leading European boiler manufacturer in the effect segment ranging from about 20 kWt to several MWt. The study shows that it is possibly to scale up the burner technology and to maintain low emissions. The boilers used in the study were designed around conventional combustion and were consequently not optimized for implementation of catalytic burners. From previous experiences it stands clear that the furnace volume can be dramatically decreased when applying catalytic combustion. In flame combustion, this volume is normally dimensioned to avoid flame impingement on cold surfaces and to facilitate completion of the gas-phase reactions. The emissions of nitrogen oxides can be reduced by decreasing the residence time in the furnace. Even with the over-dimensioned furnace used in this study, we easily reached emission values close to 35 mg/kWh. The emissions of carbon monoxide and unburned hydrocarbons were negligible (less than 5 ppmv). It is possible to decrease the emissions of nitrogen oxides further by designing the furnace/boiler around the catalytic burner, as suggested in the report. Simultaneously, the size of the boiler installation can be reduced greatly, which also will result in material savings, i.e. the production cost can be reduced. It is suggested to optimize the

Bimetallic catalysts for HI decomposition in the iodine-sulfur thermochemical cycle

International Nuclear Information System (INIS)

Wang Laijun; Hu Songzhi; Xu Lufei; Li Daocai; Han Qi; Chen Songzhe; Zhang Ping; Xu Jingming

2014-01-01

Among the different kinds of thermochemical water-splitting cycles, the iodine-sulfur (IS) cycle has attracted more and more interest because it is one of the promising candidates for economical and massive hydrogen production. However, there still exist some science and technical problems to be solved before industrialization of the IS process. One such problem is the catalytic decomposition of hydrogen iodide. Although the active carbon supported platinum has been verified to present the excellent performance for HI decomposition, it is very expensive and easy to agglomerate under the harsh condition. In order to decrease the cost and increase the stability of the catalysts for HI decomposition, a series of bimetallic catalysts were prepared and studied at INET. This paper summarized our present research advances on the bimetallic catalysts (Pt-Pd, Pd-Ir and Pt-Ir) for HI decomposition. In the course of the study, the physical properties, structure, and morphology of the catalysts were characterized by specific surface area, X-ray diffractometer; and transmission electron microscopy, respectively. The catalytic activity for HI decomposition was investigated in a fixed bed reactor under atmospheric pressure. The results show that due to the higher activity and better stability, the active carbon supported bimetallic catalyst is more potential candidate than mono metallic Pt catalyst for HI decomposition in the IS thermochemical cycle. (author)

Concentric catalytic combustor

Science.gov (United States)

Bruck, Gerald J [Oviedo, FL; Laster, Walter R [Oviedo, FL

2009-03-24

A catalytic combustor (28) includes a tubular pressure boundary element (90) having a longitudinal flow axis (e.g., 56) separating a first portion (94) of a first fluid flow (e.g., 24) from a second portion (95) of the first fluid flow. The pressure boundary element includes a wall (96) having a plurality of separate longitudinally oriented flow paths (98) annularly disposed within the wall and conducting respective portions (100, 101) of a second fluid flow (e.g., 26) therethrough. A catalytic material (32) is disposed on a surface (e.g., 102, 103) of the pressure boundary element exposed to at least one of the first and second portions of the first fluid flow.

Effect of support on the catalytic activity of manganese oxide catalyts for toluene combustion.

Science.gov (United States)

Pozan, Gulin Selda

2012-06-30

The aim of this work was to study combustion of toluene (1000ppm) over MnO(2) modified with different supports. α-Al(2)O(3) and γ-Al(2)O(3) obtained from Boehmite, γ-Al(2)O(3) (commercial), SiO(2), TiO(2) and ZrO(2) were used as commercial support materials. In view of potential interest of this process, the influence of support material on the catalytic performance was discussed. The deposition of 9.5MnO(2) was performed by impregnation over support. The catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature programmed reduction and oxidation (TPR/TPO) and thermogravimetric analysis (TGA). The catalytic tests were carried out at atmospheric pressure in a fixed-bed flow reactor. 9.5MnO(2)/α-Al(2)O(3)(B) (synthesized from Boehmite) catalyst exhibits the highest catalytic activity, over which the toluene conversion was up to 90% at a temperature of 289°C. Considering all the characterization and reaction data reported in this study, it was concluded that the manganese state and oxygen species played an important role in the catalytic activity. Copyright © 2012 Elsevier B.V. All rights reserved.

Characterization of deactivated catalytic cracking catalyst and evaluation as absorbent material

International Nuclear Information System (INIS)

Valt, R.B.G.; Kaminari, N.M.S.; Cordeiro, B.; Ponte, M.J.J.S.; Ponte, H.A.

2010-01-01

One of the main uses of catalysts in the petroleum industry is in step catalytic cracking, which after use and regeneration cycles generates large quantities of waste material. In this research the deactivated FCC catalyst was characterized before and after the electrokinetic remediation process, in order to assess the change of its structure and possible adsorptive capacity. Analyses of X-Ray Fluorescence Spectroscopy, Scanning Electron Microscopy and BET surface area measurement were performed. The analysis showed no structural change due to the process employed and that electrokinetic remediation has recovered 42% of adsorption capacity of the material, by removing about 89% of heavy metals adhered initially in the catalyst surface. (author)

Performance and stability of Pd nanostructures in an alkaline direct ethanol fuel cell

Science.gov (United States)

Carrera-Cerritos, R.; Fuentes-Ramírez, R.; Cuevas-Muñiz, F. M.; Ledesma-García, J.; Arriaga, L. G.

2014-12-01

Pd nanopolyhedral, nanobar and nanorod particles were synthesised using the polyol process and evaluated as anodes in a direct ethanol fuel cell. The materials were physico-chemically characterised by high-resolution transmission electronic microscopy (HR-TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The effect of the operation parameters (i.e., temperature and fuel ethanol concentration) on the maximum power density (MPD) and open circuit voltage (OCV) was investigated. In addition, a stability test was performed by applying three current density steps for fifty cycles. The OCV values increased as the temperature increased for all of the catalysts at low ethanol concentration. Although the MPD increased with temperature for all of the catalyst independent of the ethanol concentration, the effect of the temperature on the MPD for each Pd structure results in different slopes due to the different crystal faces. Finally, a loss of electro-catalytic activity after fifty cycles was observed in all of the catalysts evaluated, which may be in response to morphological changes in the nanostructures.

Functional tuning of the catalytic residue pKa in a de novo designed esterase.

Science.gov (United States)

Hiebler, Katharina; Lengyel, Zsófia; Castañeda, Carlos A; Makhlynets, Olga V

2017-09-01

AlleyCatE is a de novo designed esterase that can be allosterically regulated by calcium ions. This artificial enzyme has been shown to hydrolyze p-nitrophenyl acetate (pNPA) and 4-nitrophenyl-(2-phenyl)-propanoate (pNPP) with high catalytic efficiency. AlleyCatE was created by introducing a single-histidine residue (His 144 ) into a hydrophobic pocket of calmodulin. In this work, we explore the determinants of catalytic properties of AlleyCatE. We obtained the pK a value of the catalytic histidine using experimental measurements by NMR and pH rate profile and compared these values to those predicted from electrostatics pK a calculations (from both empirical and continuum electrostatics calculations). Surprisingly, the pK a value of the catalytic histidine inside the hydrophobic pocket of calmodulin is elevated as compared to the model compound pK a value of this residue in water. We determined that a short-range favorable interaction with Glu 127 contributes to the elevated pK a of His 144 . We have rationally modulated local electrostatic potential in AlleyCatE to decrease the pK a of its active nucleophile, His 144 , by 0.7 units. As a direct result of the decrease in the His 144 pK a value, catalytic efficiency of the enzyme increased by 45% at pH 6. This work shows that a series of simple NMR experiments that can be performed using low field spectrometers, combined with straightforward computational analysis, provide rapid and accurate guidance to rationally improve catalytic efficiency of histidine-promoted catalysis. Proteins 2017; 85:1656-1665. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Catalytic models developed through social work

DEFF Research Database (Denmark)

Jensen, Mogens

2015-01-01

of adolescents placed in out-of-home care and is characterised using three situated cases as empirical data. Afterwards the concept of catalytic processes is briefly presented and then applied in an analysis of pedagogical treatment in the three cases. The result is a different conceptualisation of the social......The article develops the concept of catalytic processes in relation to social work with adolescents in an attempt to both reach a more nuanced understanding of social work and at the same time to develop the concept of catalytic processes in psychology. The social work is pedagogical treatment...

Pi-activated alcohols: an emerging class of alkylating agents for catalytic Friedel-Crafts reactions.

Science.gov (United States)

Bandini, Marco; Tragni, Michele

2009-04-21

The direct functionalization of aromatic compounds, via Friedel-Crafts alkylation reactions with alcohols, is one of the cornerstones in organic chemistry. The present emerging area deals with the recent advances in the use of pi-activated alcohols in the catalytic and stereoselective construction of benzylic stereocenters.

Synthesis and characterization of magnetically recyclable Ag nanoparticles immobilized on Fe3O4@C nanospheres with catalytic activity

International Nuclear Information System (INIS)

Li, Wei-hong; Yue, Xiu-ping; Guo, Chang-sheng; Lv, Jia-pei; Liu, Si-si; Zhang, Yuan; Xu, Jian

2015-01-01

Highlights: • Ag-loaded Fe 3 O 4 @C nanospheres were synthesized by a facile method. • The Fe 3 O 4 encapsulated mesoporous carbon was decorated with 10 nm Ag nanocrystals. • The as-prepared Ag-Fe 3 O 4 @C nanocomposite showed excellent catalytic activity. • The nanocomposite had convenient magnetic separability. - Abstract: A novel approach for the synthesis of Ag-loaded Fe 3 O 4 @C nanospheres (Ag-Fe 3 O 4 @C) was successfully developed. The catalysts possessed a carbon-coated magnetic core and grew active silver nanoparticles on the outer shell using hydrazine monohydrate as the AgNO 3 reductant in ethanol. The morphology, inner structure, and magnetic properties of the as-prepared composites were studied with transmission electron microscopy (TEM), X-ray powder diffraction (XRD), fourier translation infrared spectroscopy (FT-IR), and vibrating sample magnetometer (VSM) techniques. Catalytic activity was investigated by degrading rhodamine B (RhB) in the designed experiment. The obtained products were monodispersed and bifunctional with high magnetization, as well as exhibited excellent catalytic activity toward organic dye with 98% of RhB conversion within 20 min in the presence of NaBH 4 . The product also exhibited convenient magnetic separability and maintained high catalytic activity after six cycle runs

Reduced graphene oxide wrapped Fe3O4-Co3O4 yolk-shell nanostructures for advanced catalytic oxidation based on sulfate radicals

Science.gov (United States)

Zhang, Lishu; Yang, Xijia; Han, Erfen; Zhao, Lijun; Lian, Jianshe

2017-02-01

In this work, we designed and synthesized a high performance catalyst of reduced graphene oxide (RGO) wrapped Fe3O4-Co3O4 (RGO/Fe3O4-Co3O4) yolk-shell nanostructures for advanced catalytic oxidation based on sulfate radicals. The synergistic catalytic action of the RGO/Fe3O4-Co3O4 yolk-shell nanostructures activate the peroxymonosulfate (PMS) to produce sulfate radicals (SO4rad -) for organic dyes degradation, and the Orange II can be almost completely degradated in 5 min. Meanwhile the RGO wrapping prevents the loss of cobalt in the catalytic process, and the RGO/Fe3O4-Co3O4 can be recycled after catalyzed reaction due to the presence of magnetic iron core. What's more, it can maintain almost the same high catalytic activity even after 10 cycles through repeated NaBH4 reduction treatment. Hence, RGO/Fe3O4-Co3O4 yolk-shell nanostructures possess a great opportunity to become a promising candidate for waste water treatment in industry.

Catalytically favorable surface patterns in Pt-Au nanoclusters

KAUST Repository

Mokkath, Junais Habeeb

2013-01-01

Motivated by recent experimental demonstrations of novel PtAu nanoparticles with highly enhanced catalytic properties, we present a systematic theoretical study that explores principal catalytic indicators as a function of the particle size and composition. We find that Pt electronic states in the vicinity of the Fermi level combined with a modified electron distribution in the nanoparticle due to Pt-to-Au charge transfer are the origin of the outstanding catalytic properties. From our model we deduce the catalytically favorable surface patterns that induce ensemble and ligand effects. © The Royal Society of Chemistry 2013.

Turning goals into results: the power of catalytic mechanisms.

Science.gov (United States)

Collins, J

1999-01-01

Most executives have a big, hairy, audacious goal. They write vision statements, formalize procedures, and develop complicated incentive programs--all in pursuit of that goal. In other words, with the best of intentions, they install layers of stultifying bureaucracy. But it doesn't have to be that way. In this article, Jim Collins introduces the catalytic mechanism, a simple yet powerful managerial tool that helps translate lofty aspirations into concrete reality. Catalytic mechanisms are the crucial link between objectives and performance; they are a galvanizing, nonbureaucratic means to turn one into the other. What's the difference between catalytic mechanisms and most traditional managerial controls? Catalytic mechanisms share five characteristics. First, they produce desired results in unpredictable ways. Second, they distribute power for the benefit of the overall system, often to the discomfort of those who traditionally hold power. Third, catalytic mechanisms have teeth. Fourth, they eject "viruses"--those people who don't share the company's core values. Finally, they produce an ongoing effect. Catalytic mechanisms are just as effective for reaching individual goals as they are for corporate ones. To illustrate how catalytic mechanisms work, the author draws on examples of individuals and organizations that have relied on such mechanisms to achieve their goals. The same catalytic mechanism that works in one organization, however, will not necessarily work in another. Catalytic mechanisms must be tailored to specific goals and situations. To help readers get started, the author offers some general principles that support the process of building catalytic mechanisms effectively.

Atomically Precise Metal Nanoclusters for Catalytic Application

Energy Technology Data Exchange (ETDEWEB)

Jin, Rongchao [Carnegie Mellon Univ., Pittsburgh, PA (United States)

2016-11-18

The central goal of this project is to explore the catalytic application of atomically precise gold nanoclusters. By solving the total structures of ligand-protected nanoclusters, we aim to correlate the catalytic properties of metal nanoclusters with their atomic/electronic structures. Such correlation unravel some fundamental aspects of nanocatalysis, such as the nature of particle size effect, origin of catalytic selectivity, particle-support interactions, the identification of catalytically active centers, etc. The well-defined nanocluster catalysts mediate the knowledge gap between single crystal model catalysts and real-world conventional nanocatalysts. These nanoclusters also hold great promise in catalyzing certain types of reactions with extraordinarily high selectivity. These aims are in line with the overall goals of the catalytic science and technology of DOE and advance the BES mission “to support fundamental research to understand, predict, and ultimately control matter and energy at the level of electrons, atoms, and molecules”. Our group has successfully prepared different sized, robust gold nanoclusters protected by thiolates, such as Au₂₅(SR)₁₈, Au₂₈(SR)₂₀, Au₃₈(SR)₂₄, Au₉₉(SR)₄₂, Au₁₄₄(SR)₆₀, etc. Some of these nanoclusters have been crystallographically characterized through X-ray crystallography. These ultrasmall nanoclusters (< 2 nm diameter) exhibit discrete electronic structures due to quantum size effect, as opposed to quasicontinuous band structure of conventional metal nanoparticles or bulk metals. The available atomic structures (metal core plus surface ligands) of nanoclusters serve as the basis for structure-property correlations. We have investigated the unique catalytic properties of nanoclusters (i.e. not observed in conventional nanogold catalysts) and revealed the structure-selectivity relationships. Highlights of our

Enhanced Hydrothermal Stability and Catalytic Performance of HKUST-1 by Incorporating Carboxyl-Functionalized Attapulgite.

Science.gov (United States)

Yuan, Bo; Yin, Xiao-Qian; Liu, Xiao-Qin; Li, Xing-Yang; Sun, Lin-Bing

2016-06-29

Much attention has been paid to metal-organic frameworks (MOFs) due to their large surface areas, tunable functionality, and diverse structure. Nevertheless, most reported MOFs show poor hydrothermal stability, which seriously hinders their applications. Here a strategy is adopted to tailor the properties of MOFs by means of incorporating carboxyl-functionalized natural clay attapulgite (ATP) into HKUST-1, a well-known MOF. A new type of hybrid material was thus fabricated from the hybridization of HKUST-1 and ATP. Our results indicated that the hydrothermal stability of the MOFs as well as the catalytic performance was apparently improved. The frameworks of HKUST-1 were severely destroyed after hydrothermal treatment (hot water vapor, 60 °C), while that of the hybrid materials was maintained. For the hybrid materials containing 8.4 wt % of ATP, the surface area reached 1302 m(2)·g(-1) and was even higher than that of pristine HKUST-1 (1245 m(2)·g(-1)). In the ring-opening of styrene oxide, the conversion reached 98.9% at only 20 min under catalysis from the hybrid material, which was obviously higher than that over pristine HKUST-1 (80.9%). Moreover, the hybrid materials showed excellent reusability and the catalytic activity was recoverable without loss after six cycles. Our materials provide promising candidates for heterogeneous catalysis owing to the good catalytic activity and reusability.

Design of a PWR for long cycle and direct recycling of spent fuel

Energy Technology Data Exchange (ETDEWEB)

Mohamed, Nader M.A., E-mail: mnader73@yahoo.com

2015-12-15

Highlights: • Single-batch loading PWR with a new fuel assembly for 36 calendar months cycle was designed. • The new fuel assembly is constructed from a number of CANDU fuel bundles. • This design enables to recycle the spent fuel directly in CANDU reactors for high burnup. • Around 56 MWd/kgU burnup is achieved from fuel that has average enrichment of 4.8 w/o U-235 using this strategy. • Safety parameters such as the power distribution and CANDU coolant void reactivity were considered. - Abstract: In a previous work, a new design was proposed for the Pressurized Water Reactor (PWR) fuel assembly for direct use of the PWR spent fuel without processing. The proposed assembly has four zircaloy-4 tubes contains a number of 61-element CANDU fuel bundles (8 bundles per tube) stacked end to end. The space between the tubes contains 44 lower enriched UO{sub 2} fuel rods and 12 guide tubes. In this paper, this assembly is used to build a single batch loading 36-month PWR and the spent CANDU bundles are recycled in the on power refueling CANDU reactors. The Advanced PWR (APWR) is considered as a reference design. The average enrichment in the core is 4.76%w U-235. IFBA and Gd{sub 2}O{sub 3} as burnable poisons are used for controlling the excess reactivity and to flatten the power distribution. The calculations using MCNPX showed that the PWR will discharge the fuel with average burnup of 31.8 MWd/kgU after 1000 effective full power days. Assuming a 95 days plant outage, 36 calendar months can be achieved with a capacity factor of 91.3%. Good power distribution in the core is obtained during the cycle and the required critical boron concentration is less than 1750 ppm. Recycling of the discharged CANDU fuel bundles that represents 85% of the fuel in the assembly, in CANDU-6 or in 700 MWe Advanced CANDU Reactor (ACR-700), an additional burnup of about 31 or 26 MWd/kgU burnup can be achieved, respectively. Averaging the fuel burnup on the all fuel in the PWR

Catalytic processing of high-sulfur fuels for distributed hydrogen production

Energy Technology Data Exchange (ETDEWEB)

Muradov, Nazim; Ramasamy, Karthik; Huang, Cunping; T-Raissi, Ali [Central Florida Univ., FL (United States)

2010-07-01

In this work, the development of a new on-demand hydrogen production technology is reported. In this process, a liquid hydrocarbon fuel (e.g., high-S diesel) is first catalytically pre-reformed to shorter chain gaseous hydrocarbons (predominantly, C{sub 1}-C{sub 3}) before being directed to the steam reformer, where it is converted to syngas and then to high-purity hydrogen. In the pre-reformer, most sulfurous species present in the fuel are catalytically converted to H{sub 2}S. In the desulfurization unit, H{sub 2}S is scrubbed and converted to H{sub 2} and elemental sulfur. Desulfurization of the pre-reformate gas is carried out in a special regenerative redox system, which includes Fe(II)/Fe(III)-containing aqueous phase scrubber coupled with an electrolyzer. The integrated pre-reformer/scrubber/electrolyzer unit operated successfully on high-S diesel fuel for more than 100 hours meeting the required desulfurization target of >95 % sulfur removal. (orig.)

Highly Oriented Growth of Catalytically Active Zeolite ZSM‐5 Films with a Broad Range of Si/Al Ratios

OpenAIRE

Fu, Donglong; Schmidt, Joel E.; Ristanović, Zoran; Chowdhury, Abhishek Dutta; Meirer, Florian; Weckhuysen, Bert M.

2017-01-01

Abstract Highly b‐oriented zeolite ZSM‐5 films are critical for applications in catalysis and separations and may serve as models to study diffusion and catalytic properties in single zeolite channels. However, the introduction of catalytically active Al3+ usually disrupts the orientation of zeolite films. Herein, using structure‐directing agents with hydroxy groups, we demonstrate a new method to prepare highly b‐oriented zeolite ZSM‐5 films with a broad range of Si/Al ratios (Si/Al=45 to ∞)...

MWW-type titanosilicate synthesis, structural modification and catalytic applications to green oxidations

CERN Document Server

Wu, Peng; Xu, Le; Liu, Yueming; He, Mingyuan

2013-01-01

This book provides a comprehensive review of a new generation of selective oxidation titanosilicate catalysts with the MWW topology (Ti-MWW) based on the research achievements of the past 12 years. It gives an overview of the synthesis, structure modification and catalytic properties of Ti-MWW. Ti-MWW can readily be prepared by means of direct hydrothermal synthesis with crystallization-supporting agents, using dual-structure-directing agents and a dry-gel conversion technique. It also can be post-synthesized through unique reversible structure transformation and liquid-phase isomorphous subst

Kinetic Parameters of Non-Isothermal Thermogravimetric Non-Catalytic and Catalytic Pyrolysis of Empty Fruit Bunch with Alumina by Kissinger and Ozawa Methods

Science.gov (United States)

Rahayu Mohamed, Alina; Li, Nurfahani; Sohaimi, Khairunissa Syairah Ahmad; Izzati Iberahim, Nur; Munirah Rohaizad, Nor; Hamzah, Rosniza

2018-03-01

The non-isothermal thermogravimetric non-catalytic and catalytic empty fruit bunch (EFB) pyrolysis with alumina were performed at different heating rates of 10, 15, 20, 25, 30 and 40 K/min under nitrogen atmosphere at a flow rate of 100 ml/min under dynamic conditions from 301 K to 1273 K. The activation energy were calculated based on Kissinger and Ozawa methods. Both reactions followed first order reactions. By Kissinger method, the activation energy and Ln A values for non-catalytic and catalytic EFB pyrolysis with alumina were 188.69 kJ mol-1 and 201.67 kJ/mol respectively. By Ozawa method, the activation energy values for non-catalytic and catalytic EFB pyrolysis with alumina were 189.13 kJ/mol and 201.44 kJ/mol respectively. The presence of catalyst increased the activation energy values for EFB pyrolysis as calculated by Kissinger and Ozawa methods.

Energy and exergy analysis of the Kalina cycle for use in concentrated solar power plants with direct steam generation

DEFF Research Database (Denmark)

Knudsen, Thomas; Clausen, Lasse Røngaard; Haglind, Fredrik

2014-01-01

In concentrated solar power plants using direct steam generation, the usage of a thermal storage unit based only on sensible heat may lead to large exergetic losses during charging and discharging, due to a poor matching of the temperature profiles. By the use of the Kalina cycle, in which...... evaporation and condensation takes place over a temperature range, the efficiency of the heat exchange processes can be improved, possibly resulting also in improved overall performance of the system. This paper is aimed at evaluating the prospect of using the Kalina cycle for concentrated solar power plants...... with direct steam generation. The following two scenarios were addressed using energy and exergy analysis: generating power using heat from only the receiver and using only stored heat. For each of these scenarios comparisons were made for mixture concentrations ranging from 0.1 mole fraction of ammonia to 0...

Structure and catalytic properties of metal β-diketonate complexes with oxygen-containing compounds

International Nuclear Information System (INIS)

Nizel'skij, Yu.N.; Ishchenko, S.S.; Lipatova, T.Eh.

1985-01-01

The results of researches published in recent 15-20 years of complexes of metal β-diketonates (including Cr 3+ , VO 2+ , MoOΛ2 2+ , Co 3+ , Mn 3+ , Ni 2+ , Fe 3+ ) with oxygen-containing compounds (alcohols, glycols, phenols, hydroperoxides, aldehydes, esters, etc.) playing an important role in catalytic processes of oxidation, addition, polymerization and copolymerization are reviewed. Data on the nature of chemical bond of oxygen-containing reacting agents with metal β-diketonates, on structure of metal β-diketonate complexes with oxygen-containing reacting agents and thermodynamics of complexing as well as on activation of reacting agents in complexes and catalytic properties of metal β-diketonates are discussed. Stored materials make it possible to exercise directed control of metal β-diketonate activity

Merging Visible Light Photoredox Catalysis with Metal Catalyzed C–H Activations: On the Role of Oxygen and Superoxide Ions as Oxidants

KAUST Repository

Fabry, David C.; Rueping, Magnus

2016-01-01

ConspectusThe development of efficient catalytic systems for direct aromatic C-H bond functionalization is a long-desired goal of chemists, because these protocols provide environmental friendly and waste-reducing alternatives to classical methodologies for C-C and C-heteroatom bond formation. A key challenge for these transformations is the reoxidation of the in situ generated metal hydride or low-valent metal complexes of the primary catalytic bond forming cycle. To complete the catalytic cycle and to regenerate the C-H activation catalyst, (super)stoichiometric amounts of Cu(II) or Ag(I) salts have often been applied. Recently,

Merging Visible Light Photoredox Catalysis with Metal Catalyzed C–H Activations: On the Role of Oxygen and Superoxide Ions as Oxidants

KAUST Repository

Fabry, David C.

2016-08-24

ConspectusThe development of efficient catalytic systems for direct aromatic C-H bond functionalization is a long-desired goal of chemists, because these protocols provide environmental friendly and waste-reducing alternatives to classical methodologies for C-C and C-heteroatom bond formation. A key challenge for these transformations is the reoxidation of the in situ generated metal hydride or low-valent metal complexes of the primary catalytic bond forming cycle. To complete the catalytic cycle and to regenerate the C-H activation catalyst, (super)stoichiometric amounts of Cu(II) or Ag(I) salts have often been applied. Recently,

On the study of catalytic membrane reactor for water detritiation: Modeling approach

Energy Technology Data Exchange (ETDEWEB)

Liger, Karine, E-mail: karine.liger@cea.fr [CEA, DEN, DTN/SMTA/LIPC Cadarache, Saint Paul-lez-Durance F-13108 (France); Mascarade, Jérémy [CEA, DEN, DTN/SMTA/LIPC Cadarache, Saint Paul-lez-Durance F-13108 (France); Joulia, Xavier; Meyer, Xuan-Mi [Université de Toulouse, INPT, UPS, Laboratoire de Génie Chimique, 4, Allée Emile Monso, Toulouse F-31030 (France); CNRS, Laboratoire de Génie Chimique, Toulouse F-31030 (France); Troulay, Michèle; Perrais, Christophe [CEA, DEN, DTN/SMTA/LIPC Cadarache, Saint Paul-lez-Durance F-13108 (France)

2016-11-01

Highlights: • Experimental results for the conversion of tritiated water (using deuterium as a simulant of tritium) by means of a catalytic membrane reactor in view of tritium recovery. • Phenomenological 2D model to represent catalytic membrane reactor behavior including the determination of the compositions of gaseous effluents. • Good agreement between the simulation results and experimental measurements performed on the dedicated facility. • Explanation of the unexpected behavior of the catalytic membrane reactor by the modeling results and in particular the gas composition estimation. - Abstract: In the framework of tritium recovery from tritiated water, efficiency of packed bed membrane reactors have been successfully demonstrated. Thanks to protium isotope swamping, tritium bonded water can be recovered under the valuable Q{sub 2} form (Q = H, D or T) by means of isotope exchange reactions occurring on catalyst surface. The use of permselective Pd-based membrane allows withdrawal of reactions products all along the reactor, and thus limits reverse reaction rate to the benefit of the direct one (shift effect). The reactions kinetics, which are still little known or unknown, are generally assumed to be largely greater than the permeation ones so that thermodynamic equilibriums of isotope exchange reactions are generally assumed. This paper proposes a new phenomenological 2D model to represent catalytic membrane reactor behavior with the determination of gas effluents compositions. A good agreement was obtained between the simulation results and experimental measurements performed on a dedicated facility. Furthermore, the gas composition estimation permits to interpret unexpected behavior of the catalytic membrane reactor. In the next future, further sensitivity analysis will be performed to determine the limits of the model and a kinetics study will be conducted to assess the thermodynamic equilibrium of reactions.

On the study of catalytic membrane reactor for water detritiation: Modeling approach

International Nuclear Information System (INIS)

Liger, Karine; Mascarade, Jérémy; Joulia, Xavier; Meyer, Xuan-Mi; Troulay, Michèle; Perrais, Christophe

2016-01-01

Highlights: • Experimental results for the conversion of tritiated water (using deuterium as a simulant of tritium) by means of a catalytic membrane reactor in view of tritium recovery. • Phenomenological 2D model to represent catalytic membrane reactor behavior including the determination of the compositions of gaseous effluents. • Good agreement between the simulation results and experimental measurements performed on the dedicated facility. • Explanation of the unexpected behavior of the catalytic membrane reactor by the modeling results and in particular the gas composition estimation. - Abstract: In the framework of tritium recovery from tritiated water, efficiency of packed bed membrane reactors have been successfully demonstrated. Thanks to protium isotope swamping, tritium bonded water can be recovered under the valuable Q_2 form (Q = H, D or T) by means of isotope exchange reactions occurring on catalyst surface. The use of permselective Pd-based membrane allows withdrawal of reactions products all along the reactor, and thus limits reverse reaction rate to the benefit of the direct one (shift effect). The reactions kinetics, which are still little known or unknown, are generally assumed to be largely greater than the permeation ones so that thermodynamic equilibriums of isotope exchange reactions are generally assumed. This paper proposes a new phenomenological 2D model to represent catalytic membrane reactor behavior with the determination of gas effluents compositions. A good agreement was obtained between the simulation results and experimental measurements performed on a dedicated facility. Furthermore, the gas composition estimation permits to interpret unexpected behavior of the catalytic membrane reactor. In the next future, further sensitivity analysis will be performed to determine the limits of the model and a kinetics study will be conducted to assess the thermodynamic equilibrium of reactions.

Catalytic Stereoinversion of L-Alanine to Deuterated D-Alanine.

Science.gov (United States)

Moozeh, Kimia; So, Soon Mog; Chin, Jik

2015-08-03

A combination of an achiral pyridoxal analogue and a chiral base has been developed for catalytic deuteration of L-alanine with inversion of stereochemistry to give deuterated D-alanine under mild conditions (neutral pD and 25 °C) without the use of any protecting groups. This system can also be used for catalytic deuteration of D-alanine with retention of stereochemistry to give deuterated D-alanine. Thus a racemic mixture of alanine can be catalytically deuterated to give an enantiomeric excess of deuterated D-alanine. While catalytic deracemization of alanine is forbidden by the second law of thermodynamics, this system can be used for catalytic deracemization of alanine with deuteration. Such green and biomimetic approach to catalytic stereocontrol provides insights into efficient amino acid transformations. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mechanism of Diphtheria Toxin Catalytic Domain Delivery to the Eukaryotic Cell Cytosol and the Cellular Factors that Directly Participate in the Process

Science.gov (United States)

Murphy, John R.

2011-01-01

Research on diphtheria and anthrax toxins over the past three decades has culminated in a detailed understanding of their structure function relationships (e.g., catalytic (C), transmembrane (T), and receptor binding (R) domains), as well as the identification of their eukaryotic cell surface receptor, an understanding of the molecular events leading to the receptor-mediated internalization of the toxin into an endosomal compartment, and the pH triggered conformational changes required for pore formation in the vesicle membrane. Recently, a major research effort has been focused on the development of a detailed understanding of the molecular interactions between each of these toxins and eukaryotic cell factors that play an essential role in the efficient translocation of their respective catalytic domains through the trans-endosomal vesicle membrane pore and delivery into the cell cytosol. In this review, I shall focus on recent findings that have led to a more detailed understanding of the mechanism by which the diphtheria toxin catalytic domain is delivered to the eukaryotic cell cytosol. While much work remains, it is becoming increasingly clear that the entry process is facilitated by specific interactions with a number of cellular factors in an ordered sequential fashion. In addition, since diphtheria, anthrax lethal factor and anthrax edema factor all carry multiple coatomer I complex binding motifs and COPI complex has been shown to play an essential role in entry process, it is likely that the initial steps in catalytic domain entry of these divergent toxins follow a common mechanism. PMID:22069710

A Review on Catalytic Membranes Production and Applications

Directory of Open Access Journals (Sweden)

Heba Abdallah

2017-05-01

Full Text Available The development of the chemical industry regarding reducing the production cost and obtaining a high-quality product with low environmental impact became the essential requirements of the world in these days. The catalytic membrane is considered as one of the new alternative solutions of catalysts problems in the industries, where the reaction and separation can be amalgamated in one unit. The catalytic membrane has numerous advantages such as breaking the thermodynamic equilibrium limitation, increasing conversion rate, reducing the recycle and separation costs. But the limitation or most disadvantages of catalytic membranes related to the high capital costs for fabrication or the fact that manufacturing process is still under development. This review article summarizes the most recent advances and research activities related to preparation, characterization, and applications of catalytic membranes. In this article, various types of catalytic membranes are displayed with different applications and explained the positive impacts of using catalytic membranes in various reactions. Copyright © 2017 BCREC Group. All rights reserved. Received: 1st April 2016; Revised: 14th February 2017; Accepted: 22nd February 2017 How to Cite: Abdallah, H. (2017. A Review on Catalytic Membranes Production and Applications. Bulletin of Chemical Reaction Engineering & Catalysis, 12 (2: 136-156 (doi:10.9767/bcrec.12.2.462.136-156 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.12.2.462.136-156

Enhanced catalytic activity of the nanostructured Co-W-B film catalysts for hydrogen evolution from the hydrolysis of ammonia borane.

Science.gov (United States)

Li, Chao; Wang, Dan; Wang, Yan; Li, Guode; Hu, Guijuan; Wu, Shiwei; Cao, Zhongqiu; Zhang, Ke

2018-08-15

In this work, nanostructured Co-W-B films are successfully synthesized on the foam sponge by electroless plating method and employed as the catalysts with enhanced catalytic activity towards hydrogen evolution from the hydrolysis of ammonia borane (NH 3 BH 3 , AB) at room temperature. The particle size of the as-prepared Co-W-B film catalysts is varied by adjusting the depositional pH value to identify the most suitable particle size for hydrogen evolution of AB hydrolysis. The Co-W-B film catalyst with the particle size of about 67.3 nm shows the highest catalytic activity and can reach a hydrogen generation rate of 3327.7 mL min -1 g cat -1 at 298 K. The activation energy of the hydrolysis reaction of AB is determined to be 32.2 kJ mol -1 . Remarkably, the as-obtained Co-W-B film is also a reusable catalyst preserving 78.4% of their initial catalytic activity even after 5 cycles in hydrolysis of AB at room temperature. Thus, the enhanced catalytic activity illustrates that the Co-W-B film is a promising catalyst for AB hydrolytic dehydrogenation in fuel cells and the related fields. Copyright © 2018 Elsevier Inc. All rights reserved.

Results of the German alternative fuel cycle evaluation and further efforts geared toward demonstration of direct disposal

International Nuclear Information System (INIS)

Papp, R.; Closs, K.D.

1986-01-01

In a comparative study initiated by the German Federal Ministry for Research and Technology which was carried out by Karlsruhe Nuclear Research Center in the period from 1981 to 1985, direct disposal of spent fuel was contrasted to the traditional fuel cycle with reprocessing and recycle. The results of the study did not exhibit decisive advantages of direct disposal over fuel reprocessing. Due to this face and legal requirements of the German Atomic Energy Act, the cabinet concluded to continue to adhere to fuel reprocessing as the preferred version of ''Entsorgung''. But the door was left ajar for the direct disposal alternative that, under present atomic law, is permissible for fuel for which reprocessing is neither technically feasible nor economically justified. An ambitious program has been launched in the Federal Republic of Germany (FRG), geared to bring direct disposal to a point of technical maturity

Catalytic oxidative desulfurization of diesel utilizing hydrogen peroxide and functionalized-activated carbon in a biphasic diesel-acetonitrile system

Energy Technology Data Exchange (ETDEWEB)

Haw, Kok-Giap; Bakar, Wan Azelee Wan Abu; Ali, Rusmidah; Chong, Jiunn-Fat [Department of Chemistry, Faculty of Science, Universiti Teknologi Malaysia, 81310 UTM Skudai, Johor (Malaysia); Kadir, Abdul Aziz Abdul [Department of Petroleum Engineering, Faculty of Chemical and Natural Resources Engineering, Universiti Teknologi Malaysia, 81310 UTM Skudai, Johor (Malaysia)

2010-09-15

This paper presents the development of granular functionalized-activated carbon as catalysts in the catalytic oxidative desulfurization (Cat-ODS) of commercial Malaysian diesel using hydrogen peroxide as oxidant. Granular functionalized-activated carbon was prepared from oil palm shell using phosphoric acid activation method and carbonized at 500 C and 700 C for 1 h. The activated carbons were characterized using various analytical techniques to study the chemistry underlying the preparation and calcination treatment. Nitrogen adsorption/desorption isotherms exhibited the characteristic of microporous structure with some contribution of mesopore property. The Fourier Transform Infrared Spectroscopy results showed that higher activation temperature leads to fewer surface functional groups due to thermal decomposition. Micrograph from Field Emission Scanning Electron Microscope showed that activation at 700 C creates orderly and well developed pores. Furthermore, X-ray Diffraction patterns revealed that pyrolysis has converted crystalline cellulose structure of oil palm shell to amorphous carbon structure. The influence of the reaction temperature, the oxidation duration, the solvent, and the oxidant/sulfur molar ratio were examined. The rates of the catalytic oxidative desulfurization reaction were found to increase with the temperature, and H{sub 2}O{sub 2}/S molar ratio. Under the best operating condition for the catalytic oxidative desulfurization: temperature 50 C, atmospheric pressure, 0.5 g activated carbon, 3 mol ratio of hydrogen peroxide to sulfur, 2 mol ratio of acetic acid to sulfur, 3 oxidation cycles with 1 h for each cycle using acetonitrile as extraction solvent, the sulfur content in diesel was reduced from 2189 ppm to 190 ppm with 91.3% of total sulfur removed. (author)

Fuel rich and fuel lean catalytic combustion of the stabilized confined turbulent gaseous diffusion flames over noble metal disc burners

Directory of Open Access Journals (Sweden)

Amal S. Zakhary

2014-03-01

Full Text Available Catalytic combustion of stabilized confined turbulent gaseous diffusion flames using Pt/Al2O3 and Pd/Al2O3 disc burners situated in the combustion domain under both fuel-rich and fuel-lean conditions was experimentally studied. Commercial LPG fuel having an average composition of: 23% propane, 76% butane, and 1% pentane was used. The thermal structure of these catalytic flames developed over Pt/Al2O3 and Pd/Al2O3 burners were examined via measuring the mean temperature distribution in the radial direction at different axial locations along the flames. Under-fuel-rich condition the flames operated over Pt catalytic disc attained high temperature values in order to express the progress of combustion and were found to achieve higher activity as compared to the flames developed over Pd catalytic disc. These two types of catalytic flames demonstrated an increase in the reaction rate with the downstream axial distance and hence, an increase in the flame temperatures was associated with partial oxidation towards CO due to the lack of oxygen. However, under fuel-lean conditions the catalytic flame over Pd catalyst recorded comparatively higher temperatures within the flame core in the near region of the main reaction zone than over Pt disc burner. These two catalytic flames over Pt and Pd disc burners showed complete oxidation to CO2 since the catalytic surface is covered by more rich oxygen under the fuel-lean condition.

Application of BiFeO3-based on nickel foam composites with a highly efficient catalytic activity and easily recyclable in Fenton-like process under microwave irradiation

Science.gov (United States)

Li, Shuo; Zhang, Guangshan; Zheng, Heshan; Zheng, Yongjie; Wang, Peng

2018-05-01

In this study, BiFeO3 (BFO) powders decorated on nickel foam (NF) with a high catalytic activity are prepared via a one-step microwave-assisted hydrothermal method. The factors that influence the degradation of bisphenol A (BPA) with BFO/NFs as catalysts are optimized to improve the catalytic activity in a microwave-enhanced Fenton-like process. BFO/NF exhibit a superior catalytic activity with a high BPA removal ratio (98.4%) and TOC removal ratio (69.5%) within 5 min. Results indicate that NF significantly affect the improvement of the catalytic activity of BFO because it served as a source of hydroxyl radicals (•OH) during degradation. The amount of •OH generated by BFO/NF is approximately 1.65-fold higher than that by pure BFO. After six reaction cycles, the stability and reusability of •OH remain high. These findings provide new insights into the synthesis of composites on heterogeneous catalysts with high efficiency and easy recyclability for water treatment applications.

Catalytic activity of Au nanoparticles

DEFF Research Database (Denmark)

Larsen, Britt Hvolbæk; Janssens, Ton V.W.; Clausen, Bjerne

2007-01-01

Au is usually viewed as an inert metal, but surprisingly it has been found that Au nanoparticles less than 3–5 nm in diameter are catalytically active for several chemical reactions. We discuss the origin of this effect, focusing on the way in which the chemical activity of Au may change with par......Au is usually viewed as an inert metal, but surprisingly it has been found that Au nanoparticles less than 3–5 nm in diameter are catalytically active for several chemical reactions. We discuss the origin of this effect, focusing on the way in which the chemical activity of Au may change...... with particle size. We find that the fraction of low-coordinated Au atoms scales approximately with the catalytic activity, suggesting that atoms on the corners and edges of Au nanoparticles are the active sites. This effect is explained using density functional calculations....

Influence of observed diurnal cycles of aerosol optical depth on aerosol direct radiative effect

Directory of Open Access Journals (Sweden)

A. Arola

2013-08-01

Full Text Available The diurnal variability of aerosol optical depth (AOD can be significant, depending on location and dominant aerosol type. However, these diurnal cycles have rarely been taken into account in measurement-based estimates of aerosol direct radiative forcing (ADRF or aerosol direct radiative effect (ADRE. The objective of our study was to estimate the influence of diurnal aerosol variability at the top of the atmosphere ADRE estimates. By including all the possible AERONET sites, we wanted to assess the influence on global ADRE estimates. While focusing also in more detail on some selected sites of strongest impact, our goal was to also see the possible impact regionally. We calculated ADRE with different assumptions about the daily AOD variability: taking the observed daily AOD cycle into account and assuming diurnally constant AOD. Moreover, we estimated the corresponding differences in ADREs, if the single AOD value for the daily mean was taken from the the Moderate Resolution Imaging Spectroradiometer (MODIS Terra or Aqua overpass times, instead of accounting for the true observed daily variability. The mean impact of diurnal AOD variability on 24 h ADRE estimates, averaged over all AERONET sites, was rather small and it was relatively small even for the cases when AOD was chosen to correspond to the Terra or Aqua overpass time. This was true on average over all AERONET sites, while clearly there can be much stronger impact in individual sites. Examples of some selected sites demonstrated that the strongest observed AOD variability (the strongest morning afternoon contrast does not typically result in a significant impact on 24 h ADRE. In those cases, the morning and afternoon AOD patterns are opposite and thus the impact on 24 h ADRE, when integrated over all solar zenith angles, is reduced. The most significant effect on daily ADRE was induced by AOD cycles with either maximum or minimum AOD close to local noon. In these cases, the impact on

Catalytic removal of sulfur dioxide from dibenzothiophene sulfone over Mg-Al mixed oxides supported on mesoporous silica.

Science.gov (United States)

You, Nansuk; Kim, Min Ji; Jeong, Kwang-Eun; Jeong, Soon-Yong; Park, Young-Kwon; Jeon, Jong-Ki

2010-05-01

Dibenzothiophene sulfone (DBTS), one of the products of the oxidative desulfurization of heavy oil, can be removed through extraction as well as by an adsorption process. It is necessary to utilize DBTS in conjunction with catalytic cracking. An object of the present study is to provide an Mg-Al-mesoporous silica catalyst for the removal of sulfur dioxide from DBTS. The characteristics of the Mg-Al-mesoporous silica catalyst were investigated through N2 adsorption, XRD, ICP, and XRF. An Mg-Al-mesoporous silica catalyst formulated in a direct incorporation method showed higher catalytic performance compared to pure MgO during the catalytic removal of sulfur dioxide from DBTS. The higher dispersion of Mg as well as the large surface area of the Mg-Al-mesoporous silica catalyst strongly influenced the catalyst basicity in DBTS cracking.

Catalytically stabilized combustion of lean methane-air-mixtures: a numerical model

Energy Technology Data Exchange (ETDEWEB)

Dogwiler, U; Benz, P; Mantharas, I [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

1997-06-01

The catalytically stabilized combustion of lean methane/air mixtures has been studied numerically under conditions closely resembling the ones prevailing in technical devices. A detailed numerical model has been developed for a laminar, stationary, 2-D channel flow with full heterogeneous and homogeneous reaction mechanisms. The computations provide direct information on the coupling between heterogeneous-homogeneous combustion and in particular on the means of homogeneous ignitions and stabilization. (author) 4 figs., 3 refs.

Influences of Scholarship Aid on the Social Exchange Cycle: A Qualitative Exploration of Scholarship Recipients and Direct Reciprocity

Science.gov (United States)

Forrest, Jeannie

2010-01-01

Social exchange theory asserts that individuals who receive a gift will be pressed by an internal sense of obligation to give back in turn (Mauss, 2002). While there is a great deal of literature devoted to giving, there is little literature about the receiving end of the exchange cycle. Deeply impacted by the effects of direct reciprocity are…

Engineering Metallic Nanoparticles for Enhancing and Probing Catalytic Reactions.

Science.gov (United States)

Collins, Gillian; Holmes, Justin D

2016-07-01

Recent developments in tailoring the structural and chemical properties of colloidal metal nanoparticles (NPs) have led to significant enhancements in catalyst performance. Controllable colloidal synthesis has also allowed tailor-made NPs to serve as mechanistic probes for catalytic processes. The innovative use of colloidal NPs to gain fundamental insights into catalytic function will be highlighted across a variety of catalytic and electrocatalytic applications. The engineering of future heterogenous catalysts is also moving beyond size, shape and composition considerations. Advancements in understanding structure-property relationships have enabled incorporation of complex features such as tuning surface strain to influence the behavior of catalytic NPs. Exploiting plasmonic properties and altering colloidal surface chemistry through functionalization are also emerging as important areas for rational design of catalytic NPs. This news article will highlight the key developments and challenges to the future design of catalytic NPs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrocarbon conversion with an attenuated superactive multimetallic catalytic composite

International Nuclear Information System (INIS)

Antos, G.J.

1981-01-01

Hydrocarbons are converted by contacting them at hydrocarbon conversion conditions with a novel attenuated superactive multimetallic catalytic composite comprising a combination of a catalytically effective amount of a pyrolyzed rhenium carbonyl component with a porous carrier material containing a uniform dispersion of catalytically effective amounts of a platinum group component, which is maintained in the elemental metallic state during the incorporation and pyrolysis of the rhenium carbonyl component, and of an iron component. In a highly preferred embodiment, this novel catalytic composite also contains a catalytically effective amount of a halogen component. The platinum group component, pyrolyzed rhenium carbonyl component, iron component and optional halogen component are preferably present in the multimetallic catalytic composite in amounts, calculated on an elemental basis, corresponding to about 0.01 to about 2 wt. % platinum group metal, about 0.01 to about 5 wt. % rhenium, about 0.005 to about 4 wt. % iron and about 0.1 to about 5 wt. % halogen. A key feature associated with the preparation of the subject catalytic composite is reaction of a rhenium carbonyl complex with a porous carrier material containing a uniform dispersion of an iron component and of a platinum group component maintained in the elemental state, whereby the interaction of the rhenium moiety with the platinum group moiety is maximized due to the platinophilic (i.e., platinum-seeking) propensities of the carbon monoxide ligands associated with the rhenium reagent. A specific example of the type of hydrocarbon conversion process disclosed herein is a process for the catalytic reforming of a low octane gasoline fraction wherein the gasoline fraction and a hydrogen stream are contacted with the attenuated superactive multimetallic catalytic composite at reforming conditions

Yield optimization in a cycled trickle-bed reactor: ethanol catalytic oxidation as a case study

Energy Technology Data Exchange (ETDEWEB)

Ayude, A.; Haure, P. [INTEMA, CONICET, Mar del Plata (Argentina); Cassanello, M. [Universidad de Buenos Aires, PINMATE, Departamento de Industrias, FCEyN, Buenos Aires (Argentina); Martinez, O. [Departamento de Ingenieria Quimica, FI-UNLP-CINDECA, La Plata (Argentina)

2012-05-15

The effect of slow ON-OFF liquid flow modulation on the yield of consecutive reactions is investigated for oxidation of aqueous ethanol solutions using a 0.5 % Pd/Al{sub 2}O{sub 3} commercial catalyst in a laboratory trickle-bed reactor. Experiments with modulated liquid flow rate (MLFR) were performed under the same hydrodynamic conditions (degree of wetting, liquid holdup) as experiments with constant liquid flow rate (CLFR). Thus, the impact of the duration of wet and dry cycles as well as the period can be independently investigated. Depending on cycling conditions, acetaldehyde or acetic acid production is favored with MLFR compared to CLFR. Results suggest both the opportunity and challenge of finding a way to tune the cycling parameters for producing the most appropriate product. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Direct determination of protonation states and visualization of hydrogen bonding in a glycoside hydrolase with neutron crystallography

Science.gov (United States)

Wan, Qun; Parks, Jerry M.; Hanson, B. Leif; Fisher, Suzanne Zoe; Ostermann, Andreas; Schrader, Tobias E.; Graham, David E.; Coates, Leighton; Langan, Paul; Kovalevsky, Andrey

2015-01-01

Glycoside hydrolase (GH) enzymes apply acid/base chemistry to catalyze the decomposition of complex carbohydrates. These ubiquitous enzymes accept protons from solvent and donate them to substrates at close to neutral pH by modulating the pKa values of key side chains during catalysis. However, it is not known how the catalytic acid residue acquires a proton and transfers it efficiently to the substrate. To better understand GH chemistry, we used macromolecular neutron crystallography to directly determine protonation and ionization states of the active site residues of a family 11 GH at multiple pD (pD = pH + 0.4) values. The general acid glutamate (Glu) cycles between two conformations, upward and downward, but is protonated only in the downward orientation. We performed continuum electrostatics calculations to estimate the pKa values of the catalytic Glu residues in both the apo- and substrate-bound states of the enzyme. The calculated pKa of the Glu increases substantially when the side chain moves down. The energy barrier required to rotate the catalytic Glu residue back to the upward conformation, where it can protonate the glycosidic oxygen of the substrate, is 4.3 kcal/mol according to free energy simulations. These findings shed light on the initial stage of the glycoside hydrolysis reaction in which molecular motion enables the general acid catalyst to obtain a proton from the bulk solvent and deliver it to the glycosidic oxygen. PMID:26392527

Culture in cycles: considering H.T. Odum's 'information cycle'

Science.gov (United States)

Abel, Thomas

2014-01-01

'Culture' remains a conundrum in anthropology. When recast in the mold of 'information cycles,' culture is transformed. New fault lines appear. Information is splintered into parallel or nested forms. Dynamics becomes cycling. Energy is essential. And culture has function in a directional universe. The 'information cycle' is the crowning component of H.T. Odum's theory of general systems. What follows is an application of the information cycle to the cultural domains of discourse, social media, ritual, education, journalism, technology, academia, and law, which were never attempted by Odum. In information cycles, cultural information is perpetuated - maintained against Second Law depreciation. Conclusions are that culture is in fact a nested hierarchy of cultural forms. Each scale of information production is semi-autonomous, with its own evolutionary dynamics of production and selection in an information cycle. Simultaneously, each information cycle is channeled or entrained by its larger scale of information and ultimately human-ecosystem structuring.

Catalytic treatment

Energy Technology Data Exchange (ETDEWEB)

Bindley, W T.R.

1931-04-18

An apparatus is described for the catalytic treatment of liquids, semi-liquids, and gases comprising a vessel into which the liquid, semi-liquid, or gas to be treated is introduced through a common inlet to a chamber within the vessel whence it passes to contact with a catalyst through radially arranged channels or passages to a common outlet chamber.

Novel catalytic micromotor of porous zeolitic imidazolate framework-67 for precise drug delivery.

Science.gov (United States)

Wang, Linlin; Zhu, Hongli; Shi, Ying; Ge, You; Feng, Xiaomiao; Liu, Ruiqing; Li, Yi; Ma, Yanwen; Wang, Lianhui

2018-06-07

Micromotors hold promise as drug carriers for targeted drug delivery owing to the characteristics of self-propulsion and directional navigation. However, several defects still exist, including high cost, short movement life, low drug loading and slow release rate. Herein, a novel catalytic micromotor based on porous zeolitic imidazolate framework-67 (ZIF-67) synthesized by a greatly simplified wet chemical method assisted with ultrasonication is described as an efficient anticancer drug carrier. These porous micromotors display effective autonomous motion in hydrogen peroxide and long durable movement life of up to 90 min. Moreover, the multifunctional micromotor ZIF-67/Fe3O4/DOX exhibits excellent performance in precise drug delivery under external magnetic field with high drug loading capacity of fluorescent anticancer drug DOX up to 682 μg mg-1 owing to its porous nature, high surface area and rapid drug release based on dual stimulus of catalytic reaction and solvent effects. Therefore, these porous ZIF-67-based catalytic micromotors combine the domains of metal-organic frameworks (MOFs) and micomotors, thus developing potential resources for micromotors and holding great potential as label-free and precisely controlled high-quality candidates of drug delivery systems for biomedical applications.

Catalytic cleavage activities of 10–23 DNAzyme analogs functionalized with an amino group in its catalytic core

Directory of Open Access Journals (Sweden)

Qi Wang

2012-02-01

Full Text Available Functionalization of the catalytic loop of 10–23 DNAzyme with an amino group was performed by incorporation of 7-(3-aminopropyl-8-aza-7-deaza-2′-deoxyadenosine in different single positions. Among the nine modified positions in the catalytic loop, A9 is the unique position with positive contribution by such modification. These results indicated that more efficient deoxyribozymes remain to be explored by introduction of exogenous functional groups in an appropriate position in the catalytic loop of 10–23 DNAzyme, such as the combination of 7-functional group substituted 8-aza-7-deaza-2′-deoxyadenosine analogs and A9 position.

Molecular biological mechanism II. Molecular mechanisms of cell cycle regulation

International Nuclear Information System (INIS)

Jung, T.

2000-01-01

The cell cycle in eukaryotes is regulated by central cell cycle controlling protein kinase complexes. These protein kinase complexes consist of a catalytic subunit from the cyclin-dependent protein kinase family (CDK), and a regulatory subunit from the cyclin family. Cyclins are characterised by their periodic cell cycle related synthesis and destruction. Each cell cycle phase is characterised by a specific set of CDKs and cyclins. The activity of CDK/cyclin complexes is mainly regulated on four levels. It is controlled by specific phosphorylation steps, the synthesis and destruction of cyclins, the binding of specific inhibitor proteins, and by active control of their intracellular localisation. At several critical points within the cell cycle, named checkpoints, the integrity of the cellular genome is monitored. If damage to the genome or an unfinished prior cell cycle phase is detected, the cell cycle progression is stopped. These cell cycle blocks are of great importance to secure survival of cells. Their primary importance is to prevent the manifestation and heritable passage of a mutated genome to daughter cells. Damage sensing, DNA repair, cell cycle control and apoptosis are closely linked cellular defence mechanisms to secure genome integrity. Disregulation in one of these defence mechanisms are potentially correlated with an increased cancer risk and therefore in at least some cases with an increased radiation sensitivity. (orig.) [de

[Mechanism of catalytic ozonation for the degradation of paracetamol by activated carbon].

Science.gov (United States)

Wang, Jia-Yu; Dai, Qi-Zhou; Yu, Jie; Yan, Yi-Zhou; Chen, Jian-Meng

2013-04-01

The degradation of paracetamol (APAP) in aqueous solution was studied with ozonation integrated with activated carbon (AC). The synergistic effect of ozonation/AC process was explored by comparing the degradation efficiency of APAP in three processes (ozonation alone, activated carbon alone and ozonation integrated with activated carbon). The operational parameters that affected the reaction rate were carefully optimized. Based on the intermediates detected, the possible pathway for catalytic degradation was discussed and the reaction mechanism was also investigated. The results showed that the TOC removal reached 55.11% at 60 min in the AC/O3 system, and was significantly better than the sum of ozonation alone (20.22%) and activated carbon alone (27.39%), showing the great synergistic effect. And the BOD5/COD ratio increased from 0.086 (before reaction) to 0.543 (after reaction), indicating that the biodegradability was also greatly improved. The effects of the initial concentration of APAP, pH value, ozone dosage and AC dosage on the variation of reaction rate were carefully discussed. The catalytic reaction mechanism was different at different pH values: the organic pollutions were removed by adsorption and direct ozone oxidation at acidic pH, and mainly by catalytic ozonation at alkaline pH.

[Degradation of m-Cresol with Fe-MCM-41 in Catalytic Ozonation].

Science.gov (United States)

Sun, Wen-jing; Wang, Ya-min; Wei, Huang-zhao; Wang, Sen; Li, Xu-ning; Li, Jing-mei; Sun, Cheng-lin; An, Lu-yang

2015-04-01

Fe-MCM-41 was first used for the treatment of m-cresol in catalytic ozonation. The effect of the percentage of Fe dopping mass, catalyst dosage and the natural concentration of substrate on m-cresol conversion and TOC removal were studied. The structural property of Fe-MCM-41 was characterized by X-ray diffraction, temperature-programmed reduction, Mössbauer spectra and BET of catalysts. The results showed that Fe dopping mass had a great effect on the catalytic activity of Fe-MCM-41 in catalytic ozonation and the optimal percentage of dopping mass was 4.4% (wt). The results showed that with Fe dopping mass increase, the degree of crystallinity became weaker, the crystal surface distance reduced, as well as the specific surface area, pore volume and aperture. γ-Fe2O3 was the only form staying on the surface of MCM-41, and the catalyst had good ferromagnetism and stability. Ozonation played a role of both direct oxidation and indirect oxidation in the reaction, approximately the same ratio. Under the experimental condition of the natural pH of model wastewater,using 4.4% (wt) Fe-MCM-41 as catalyst, natural concentration of m-cresol 500 mg x L(-1), catalyst dosage 0.1 g x L(-1) and reaction time 30 min, m-cresol conversion and TOC removal were 100% and 26.8%, respectively.

Highly Efficient Catalytic Cyclic Carbonate Formation by Pyridyl Salicylimines.

Science.gov (United States)

Subramanian, Saravanan; Park, Joonho; Byun, Jeehye; Jung, Yousung; Yavuz, Cafer T

2018-03-21

Cyclic carbonates as industrial commodities offer a viable nonredox carbon dioxide fixation, and suitable heterogeneous catalysts are vital for their widespread implementation. Here, we report a highly efficient heterogeneous catalyst for CO 2 addition to epoxides based on a newly identified active catalytic pocket consisting of pyridine, imine, and phenol moieties. The polymeric, metal-free catalyst derived from this active site converts less-reactive styrene oxide under atmospheric pressure in quantitative yield and selectivity to the corresponding carbonate. The catalyst does not need additives, solvents, metals, or co-catalysts, can be reused at least 10 cycles without the loss of activity, and scaled up easily to a kilogram scale. Density functional theory calculations reveal that the nucleophilicity of pyridine base gets stronger due to the conjugated imines and H-bonding from phenol accelerates the reaction forward by stabilizing the intermediate.

Carbon nanofibers: a versatile catalytic support

Directory of Open Access Journals (Sweden)

Nelize Maria de Almeida Coelho

2008-09-01

Full Text Available The aim of this article is present an overview of the promising results obtained while using carbon nanofibers based composites as catalyst support for different practical applications: hydrazine decomposition, styrene synthesis, direct oxidation of H2S into elementary sulfur and as fuel-cell electrodes. We have also discussed some prospects of the use of these new materials in total combustion of methane and in ammonia decomposition. The macroscopic carbon nanofibers based composites were prepared by the CVD method (Carbon Vapor Deposition employing a gaseous mixture of hydrogen and ethane. The results showed a high catalytic activity and selectivity in comparison to the traditional catalysts employed in these reactions. The fact was attributed, mainly, to the morphology and the high external surface of the catalyst support.

WD40 domain of Apc1 is critical for the coactivator-induced allosteric transition that stimulates APC/C catalytic activity.

Science.gov (United States)

Li, Qiuhong; Chang, Leifu; Aibara, Shintaro; Yang, Jing; Zhang, Ziguo; Barford, David

2016-09-20

The anaphase-promoting complex/cyclosome (APC/C) is a large multimeric cullin-RING E3 ubiquitin ligase that orchestrates cell-cycle progression by targeting cell-cycle regulatory proteins for destruction via the ubiquitin proteasome system. The APC/C assembly comprises two scaffolding subcomplexes: the platform and the TPR lobe that together coordinate the juxtaposition of the catalytic and substrate-recognition modules. The platform comprises APC/C subunits Apc1, Apc4, Apc5, and Apc15. Although the role of Apc1 as an APC/C scaffolding subunit has been characterized, its specific functions in contributing toward APC/C catalytic activity are not fully understood. Here, we report the crystal structure of the N-terminal domain of human Apc1 (Apc1N) determined at 2.2-Å resolution and provide an atomic-resolution description of the architecture of its WD40 (WD40 repeat) domain (Apc1(WD40)). To understand how Apc1(WD40) contributes to APC/C activity, a mutant form of the APC/C with Apc1(WD40) deleted was generated and evaluated biochemically and structurally. We found that the deletion of Apc1(WD40) abolished the UbcH10-dependent ubiquitination of APC/C substrates without impairing the Ube2S-dependent ubiquitin chain elongation activity. A cryo-EM structure of an APC/C-Cdh1 complex with Apc1(WD40) deleted showed that the mutant APC/C is locked into an inactive conformation in which the UbcH10-binding site of the catalytic module is inaccessible. Additionally, an EM density for Apc15 is not visible. Our data show that Apc1(WD40) is required to mediate the coactivator-induced conformational change of the APC/C that is responsible for stimulating APC/C catalytic activity by promoting UbcH10 binding. In contrast, Ube2S activity toward APC/C substrates is not dependent on the initiation-competent conformation of the APC/C.

Uniformity index measurement technology using thermocouples to improve performance in urea-selective catalytic reduction systems

Science.gov (United States)

Park, Sangki; Oh, Jungmo

2018-05-01

The current commonly used nitrogen oxides (NOx) emission reduction techniques employ hydrocarbons (HCs), urea solutions, and exhaust gas emissions as the reductants. Two of the primary denitrification NOx (DeNOx) catalyst systems are the HC-lean NOx trap (HC-LNT) catalyst and urea-selective catalytic reduction (urea-SCR) catalyst. The secondary injection method depends on the type of injector, injection pressure, atomization, and spraying technique. In addition, the catalyst reaction efficiency is directly affected by the distribution of injectors; hence, the uniformity index (UI) of the reductant is very important and is the basis for system optimization. The UI of the reductant is an indicator of the NOx conversion efficiency (NCE), and good UI values can reduce the need for a catalyst. Therefore, improving the UI can reduce the cost of producing a catalytic converter, which are expensive due to the high prices of the precious metals contained therein. Accordingly, measurement of the UI is an important process in the development of catalytic systems. Two of the commonly used methods for measuring the reductant UI are (i) measuring the exhaust emissions at many points located upstream/downstream of the catalytic converter and (ii) acquisition of a reductant distribution image on a section of the exhaust pipe upstream of the catalytic converter. The purpose of this study is to develop a system and measurement algorithms to measure the exothermic response distribution in the exhaust gas as the reductant passes through the catalytic converter of the SCR catalyst system using a set of thermocouples downstream of the SCR catalyst. The system is used to measure the reductant UI, which is applied in real-time to the actual SCR system, and the results are compared for various types of mixtures for various engine operating conditions and mixer types in terms of NCE.

Study on thermodynamic cycle of high temperature gas-cooled reactor

International Nuclear Information System (INIS)

Qu Xinhe; Yang Xiaoyong; Wang Jie

2017-01-01

The development trend of the (very) High temperature gas-cooled reactor is to gradually increase the reactor outlet temperature. The different power conversion units are required at the different reactor outlet temperature. In this paper, for the helium turbine direct cycle and the combined cycle of the power conversion unit of the High temperature gas-cooled reactor, the mathematic models are established, and three cycle plans are designed. The helium turbine direct cycle is a Brayton cycle with recuperator, precooler and intercooler. In the combined cycle plan 1, the topping cycle is a simple Brayton cycle without recuperator, precooler and intercooler, and the bottoming cycle is based on the steam parameters (540deg, 6 MPa) recommended by Siemens. In the combined cycle plan 2, the topping cycle also is a simple Brayton cycle, and the bottoming cycle which is a Rankine cycle with reheating cycle is based on the steam parameters of conventional subcritical thermal power generation (540degC, 18 MPa). The optimization results showed that the cycle efficiency of the combined cycle plan 2 is the highest, the second is the helium turbine direct cycle, and the combined cycle plan 2 is the lowest. When the reactor outlet temperature is 900degC and the pressure ratio is 2.02, the cycle efficiency of the combined cycle plan 2 can reach 49.7%. The helium turbine direct cycle has a reactor inlet temperature above 500degC due to the regenerating cycle, so it requires a cooling circuit for the internal wall of the reactor pressure vessel. When the reactor outlet temperature increases, the increase of the pressure ratio required by the helium turbine direct cycle increases may bring some difficulties to the design and manufacture of the magnetic bearings. For the combined cycle, the reactor inlet temperature can be controlled below than 370degC, so the reactor pressure vessel can use SA533 steel without cooling the internal wall of the reactor pressure vessel. The pressure

Population exposure from the fuel cycle: Review and future direction

International Nuclear Information System (INIS)

Richmond, C.R.

1987-01-01

The legacy of radiation exposures confronting man arises from two historical sources of energy, the sun and radioactive decay. Contemporary man continues to be dependent on these two energy sources, which include the nuclear fuel cycle. Radiation exposures from all energy sources should be examined, with particular emphasis on the nuclear fuel cycle, incidents such as Chernobyl and Three Mile Island. In addition to risk estimation, concepts such as de minimis, life shortening as a measure of risk, and competing risks as projected into the future must be considered in placing radiation exposures in perspective. The utility of these concepts is in characterizing population exposures for decision makers in a manner that the public may judge acceptable. All these viewpoints are essential in the evaluation of population exposure from the nuclear fuel cycle

Electrooxidation of borohydride on platinum and gold electrodes: implications for direct borohydride fuel cells

International Nuclear Information System (INIS)

Gyenge, Elod

2004-01-01

The electrochemical oxidation of BH 4 - in 2 M NaOH on Pt and Au (i.e. catalytic and non-catalytic electrodes, respectively, for BH 4 - hydrolysis accompanied by H 2 evolution) has been studied by cyclic voltammetry, chrono-techniques (i.e., potentiometry, amperometry, coulometry) and electrochemical impedance spectroscopy. In the case of Pt the cyclic voltammetry behaviour of BH 4 - is influenced by both, the catalytic hydrolysis of BH 4 - yielding H 2 (followed by electrooxidation of the latter at peak potentials between -0.7 and -0.9 V versus Ag/AgCl, KCl std ) and direct oxidation of BH 4 - at more positive potentials, i.e., between -0.15 and -0.05 V. Thiourea (TU, 1.5x10 -3 M) was an effective inhibitor of the catalytic hydrolysis associated with BH 4 - electrooxidation on Pt. Therefore, in the presence of TU, only the direct oxidation of BH 4 - has been detected, with peak potentials between -0.2 and 0 V. It is proposed that TU could improve the BH 4 - utilization efficiency and the coulombic efficiency of direct borohydride fuel cells using catalytic anodes. The electrooxidation of BH 4 - on Pt/TU is an overall four-electron process, instead of the maximum eight electrons reported for Au, and it is affected by adsorbed species such as BH 4 - (fractional surface coverage ∼0.3), TU and possibly reaction intermediates

Superior acidic catalytic activity and stability of Fe-doped HTaWO6 nanotubes

KAUST Repository

Liu, He

2017-07-26

Fe-doped HTaWO6 (H1-3xFexTaWO6, x = 0.23) nanotubes as highly active solid acid catalysts were prepared via an exfoliation-scrolling-exchange process. The specific surface area and pore volume of undoped nanotubes (20.8 m2 g-1, 0.057 cm3 g-1) were remarkably enhanced through Fe3+ ion-exchange (>100 m2 g-1, 0.547 cm3 g-1). Doping Fe ions into the nanotubes endowed them with improved thermal stability due to the stronger interaction between the intercalated Fe3+ ions and the host layers. This interaction also facilitated the preservation of effective Brønsted acid sites and the generation of new acid sites. The integration of these functional roles resulted in Fe-doped nanotubes with high acidic catalytic activities in the Friedel-Crafts alkylation of anisole and the esterification of acetic acid. Facile accessibility to active sites, generation of effective Brønsted acid sites, high stability of the tubular structure and strong acid sites were found to synergistically contribute to the excellent acidic catalytic efficiency. Additionally, the activity of cycled nanocatalysts can be easily recovered through annealing treatment.

Superior acidic catalytic activity and stability of Fe-doped HTaWO6 nanotubes

KAUST Repository

Liu, He; Zhang, Haitao; Fei, Linfeng; Ma, Hongbin; Zhao, Guoying; Mak, CheeLeung; Zhang, Xixiang; Zhang, Suojiang

2017-01-01

Fe-doped HTaWO6 (H1-3xFexTaWO6, x = 0.23) nanotubes as highly active solid acid catalysts were prepared via an exfoliation-scrolling-exchange process. The specific surface area and pore volume of undoped nanotubes (20.8 m2 g-1, 0.057 cm3 g-1) were remarkably enhanced through Fe3+ ion-exchange (>100 m2 g-1, 0.547 cm3 g-1). Doping Fe ions into the nanotubes endowed them with improved thermal stability due to the stronger interaction between the intercalated Fe3+ ions and the host layers. This interaction also facilitated the preservation of effective Brønsted acid sites and the generation of new acid sites. The integration of these functional roles resulted in Fe-doped nanotubes with high acidic catalytic activities in the Friedel-Crafts alkylation of anisole and the esterification of acetic acid. Facile accessibility to active sites, generation of effective Brønsted acid sites, high stability of the tubular structure and strong acid sites were found to synergistically contribute to the excellent acidic catalytic efficiency. Additionally, the activity of cycled nanocatalysts can be easily recovered through annealing treatment.

Catalytic Reduction of NO and NOx Content in Tobacco Smoke

Directory of Open Access Journals (Sweden)

Cvetkovic N

2014-12-01

Full Text Available In order to reduce the nitric oxide (NO and nitrogen oxides (NO content in mainstream tobacco smoke, a new class of catalyst based on Cu-ZSM-5 zeolite has been synthesized. The effectiveness of the new catalyst (degree of reduction and specific catalytic ability was tested both by adding Cu-ZSM-5 zeolite directly to the tobacco blend and by addition to the filter. We have determined that adding the catalyst to the tobacco blend does not cause any changes in the physical, chemical or organoleptic properties of the cigarette blend. But, the addition reduces the yield of nitrogen oxides while having no influence on nicotine and “tar” content in the tobacco smoke of the modified blend. The catalyst addition increases the static burning rate (SBR. The changes in the quantity of NO and NOmay be explained by changes in burning conditions due to the increase of Oobtained from catalytic degradation of NO and NO, and adsorptive and diffusive properties of the catalyst. The changes in mainstream smoke analytes are also given on a puff-by-puff basis.

Thermodynamic analysis of a nuclear-hydrogen power system using H2/O2 direct combustion product as a working substance in the bottom cycle

International Nuclear Information System (INIS)

Chen, D.Z.; Yu, C.P.

1990-01-01

A combined thermodynamic cycle using nuclear and hydrogen energy as heat sources was investigated in this paper. The cycle is composed of top cycle using HTGR as energy source and helium as working medium and a bottom cycle with H 2 /O 2 direct combustion product as working substance. hydrogen and oxygen are thermochemically by splitting of water produced through a part of nuclear heat recovered from the top cycle. They may be delivered to the O 2 /H 2 users or used as fuels for the high temperature bottom Rankine steam cycle. The combined cycle not only uses the new energy sources instead of conventional fossil fuels but it possess the advantages of both helium and steam cycle. It has a high thermal efficiency, large unit capacity, many-sided usage and less pollution. It may represent a new type of combined cycles for future energy conversion and power generation. Using computer diagram, a variety of schemes were calculated and analyzed. The influence of some main parameters upon the cycle performance were also studied

Intramolecular Crosstalk between Catalytic Activities of Receptor Kinases

KAUST Repository

Kwezi, Lusisizwe

2018-01-22

Signal modulation is important for the growth and development of plants and this process is mediated by a number of factors including physiological growth regulators and their associated signal transduction pathways. Protein kinases play a central role in signaling, including those involving pathogen response mechanisms. We previously demonstrated an active guanylate cyclase (GC) catalytic center in the brassinosteroid insensitive receptor (AtBRI1) within an active intracellular kinase domain resulting in dual enzymatic activity. Here we propose a novel type of receptor architecture that is characterized by a functional GC catalytic center nested in the cytosolic kinase domain enabling intramolecular crosstalk. This may be through a cGMP-AtBRI1 complex forming that may induce a negative feedback mechanism leading to desensitisation of the receptor, regulated through the cGMP production pathway. We further argue that the comparatively low but highly localized cGMP generated by the GC in response to a ligand is sufficient to modulate the kinase activity. This type of receptor therefore provides a molecular switch that directly and/or indirectly affects ligand dependent phosphorylation of downstream signaling cascades and suggests that subsequent signal transduction and modulation works in conjunction with the kinase in downstream signaling.

Intramolecular Crosstalk between Catalytic Activities of Receptor Kinases

KAUST Repository

Kwezi, Lusisizwe; Wheeler, Janet I; Marondedze, Claudius; Gehring, Christoph A; Irving, Helen R

2018-01-01

Signal modulation is important for the growth and development of plants and this process is mediated by a number of factors including physiological growth regulators and their associated signal transduction pathways. Protein kinases play a central role in signaling, including those involving pathogen response mechanisms. We previously demonstrated an active guanylate cyclase (GC) catalytic center in the brassinosteroid insensitive receptor (AtBRI1) within an active intracellular kinase domain resulting in dual enzymatic activity. Here we propose a novel type of receptor architecture that is characterized by a functional GC catalytic center nested in the cytosolic kinase domain enabling intramolecular crosstalk. This may be through a cGMP-AtBRI1 complex forming that may induce a negative feedback mechanism leading to desensitisation of the receptor, regulated through the cGMP production pathway. We further argue that the comparatively low but highly localized cGMP generated by the GC in response to a ligand is sufficient to modulate the kinase activity. This type of receptor therefore provides a molecular switch that directly and/or indirectly affects ligand dependent phosphorylation of downstream signaling cascades and suggests that subsequent signal transduction and modulation works in conjunction with the kinase in downstream signaling.

Progress in catalytic naphtha reforming process: A review

International Nuclear Information System (INIS)

Rahimpour, Mohammad Reza; Jafari, Mitra; Iranshahi, Davood

2013-01-01

Catalytic naphtha reforming process is a vital process for refineries due to the production of high-octane components, which is intensely demanded in our modern life. The significance of this industrial process induced researchers to investigate different aspects of catalytic naphtha reforming process intensively. Some of the investigators try to improve this process by representing more effective catalysts, while others try to elucidate its kinetic and deactivation mechanisms and design more efficient reactor setups. The amount of these established papers is so much that may confuse some of the researchers who want to find collective information about catalytic naphtha reforming process. In the present paper, the published studies from 1949 until now are categorized into three main groups including finding suitable catalyst, revealing appropriate kinetic and deactivation model, and suggesting efficient reactor configuration and mode of operation. These studies are reviewed separately, and a suitable reference is provided for those who want to have access to generalized information about catalytic naphtha reforming process. Finally, various suggestions for revamping the catalytic naphtha reforming process have been proposed as a guideline for further investigations

Environmentally benign synthesis of amides and ureas via catalytic dehydrogenation coupling of volatile alcohols and amines in a Pd-Ag membrane reactor

KAUST Repository

Chen, Tao

2016-05-31

In this study, we report the direct synthesis of amides and ureas via the catalytic dehydrogenation of volatile alcohols and amines using the Milstein catalyst in a Pd-Ag/ceramic membrane reactor. A series of amides and ureas, which could not be synthesized in an open system by catalytic dehydrogenation coupling, were obtained in moderate to high yields via catalytic dehydrogenation of volatile alcohols and amines. This process could be monitored by the hydrogen produced. Compared to the traditional method of condensation, this catalytic system avoids the stoichiometric pre-activation or in situ activation of reagents, and is a much cleaner process with high atom economy. This methodology, only possible by employing the Pd-Ag/ceramic membrane reactor, not only provides a new environmentally benign synthetic approach of amides and ureas, but is also a potential method for hydrogen storage.

Environmentally benign synthesis of amides and ureas via catalytic dehydrogenation coupling of volatile alcohols and amines in a Pd-Ag membrane reactor

KAUST Repository

Chen, Tao; Zeng, Gaofeng; Lai, Zhiping; Huang, Kuo-Wei

2016-01-01

In this study, we report the direct synthesis of amides and ureas via the catalytic dehydrogenation of volatile alcohols and amines using the Milstein catalyst in a Pd-Ag/ceramic membrane reactor. A series of amides and ureas, which could not be synthesized in an open system by catalytic dehydrogenation coupling, were obtained in moderate to high yields via catalytic dehydrogenation of volatile alcohols and amines. This process could be monitored by the hydrogen produced. Compared to the traditional method of condensation, this catalytic system avoids the stoichiometric pre-activation or in situ activation of reagents, and is a much cleaner process with high atom economy. This methodology, only possible by employing the Pd-Ag/ceramic membrane reactor, not only provides a new environmentally benign synthetic approach of amides and ureas, but is also a potential method for hydrogen storage.

A novel microalgal system for energy production with nitrogen cycling

Energy Technology Data Exchange (ETDEWEB)

Minowa, T.; Sawayama, S. [National Institute for Resources and Environment, Tsukuba (Japan)

1999-08-01

A microalga, Chlorella vulgaris, could grow in the recovered solution from the low temperature catalytic gasification of itself, by which methane rich fuel gas was obtained. All nitrogen in the microalga was converted to ammonia during the gasification, and the recovered solution, in which ammonia was dissolved, could be used as nitrogen nutrient. The result of the energy evaluation indicated that the novel microalgal system for energy production with nitrogen cycling could be created. 9 refs., 3 tabs.

Catalytically favorable surface patterns in Pt-Au nanoclusters

KAUST Repository

Mokkath, Junais Habeeb; Schwingenschlö gl, Udo

2013-01-01

Motivated by recent experimental demonstrations of novel PtAu nanoparticles with highly enhanced catalytic properties, we present a systematic theoretical study that explores principal catalytic indicators as a function of the particle size

Catalytic Aminohalogenation of Alkenes and Alkynes.

Science.gov (United States)

Chemler, Sherry R; Bovino, Michael T

2013-06-07

Catalytic aminohalogenation methods enable the regio- and stereoselective vicinal difunctionalization of alkynes, allenes and alkenes with amine and halogen moieties. A range of protocols and reaction mechanisms including organometallic, Lewis base, Lewis acid and Brønsted acid catalysis have been disclosed, enabling the regio- and stereoselective synthesis of halogen-functionalized acyclic amines and nitrogen heterocycles. Recent advances including aminofluorination and catalytic enantioselective aminohalogenation reactions are summarized in this review.

Design of generic coal conversion facilities: Process release---Direct coal liquefaction

Energy Technology Data Exchange (ETDEWEB)

1991-09-01

The direct liquefaction portion of the PETC generic direct coal liquefaction process development unit (PDU) is being designed to provide maximum operating flexibility. The PDU design will permit catalytic and non-catalytic liquefaction concepts to be investigated at their proof-of-the-concept stages before any larger scale operations are attempted. The principal variations from concept to concept are reactor configurations and types. These include thermal reactor, ebullating bed reactor, slurry phase reactor and fixed bed reactor, as well as different types of catalyst. All of these operating modes are necessary to define and identify the optimum process conditions and configurations for determining improved economical liquefaction technology.

The effect of oxygen storage capacity on the dynamic characteristics of an automotive catalytic converter

International Nuclear Information System (INIS)

Shamim, Tariq

2008-01-01

Automotive catalytic converters, which are employed to reduce engine exhaust emissions, are subjected to highly transient conditions during a typical driving cycle. These transient conditions arise from changes in driving mode, the hysteresis and flow lags of the feedback control system, and result in fluctuations of air-fuel ratio, exhaust gas flow rates and temperatures. The catalyst performance is also strongly influenced by the oxygen storage capacity. This paper presents a computational investigation of the effect of oxygen storage capacity on the dynamic behavior of an automotive catalytic converter subjected to modulations in exhaust gases. The modulations are generated by forcing the temporal variations in exhaust gases air-fuel ratio, gas flow rates and temperatures. The study employs a single-channel based, one-dimensional, non-adiabatic model. The results show that the imposed modulations cause a significant departure in the catalyst behavior from its steady behavior, and the oxygen storage capacity plays an important role in determining the catalyst's response to the imposed modulations. Modulations and oxygen storage capacity are found to have relatively greater influence on the catalyst's performance near stoichiometric conditions

Systems design of direct-cycle supercritical-water-cooled fast reactors

International Nuclear Information System (INIS)

Oka, Yoshiaki; Koshizuka, Seiichi; Jevremovic, Tatjana; Okano, Yashushi

1995-01-01

The system design of a direct-cycle supercritical-water-cooled fast reactor is presented. The supercritical water does not exhibit a change of phase. the recirculation system, steam separator, and dryer of a boiling water reactor (BWR) are unnecessary. Roughly speaking, the reactor pressure vessel and control rods are similar to those of a pressurized water reactor, the containment and emergency core cooling system are similar to a BWR, and the balance of plant is similar to a supercritical-pressure fossil-fired power plant (FPP). the electric power of the fast converter is 1,508 MW(electric). The number of coolant loops is only two because of the high coolant enthalpy. Containment volume is much reduced. The thermal efficiency is improved 24% over a BWR. The coolant void reactivity is negative by placing thin zirconium-hydride layers between seeds and blankets. The power costs would be much reduced compared with those of a light water reactor (LWR) and a liquid-metal fast breeder reactor. The concept is based on the huge amount of experience with the water coolant technology of LWRs and FPPs. The oxidation of stainless steel cladding is avoided by adopting a much lower coolant temperature than that of the FPP

Nanostructured, mesoporous Au/TiO2 model catalysts – structure, stability and catalytic properties

Directory of Open Access Journals (Sweden)

Matthias Roos

2011-09-01

Full Text Available Aiming at model systems with close-to-realistic transport properties, we have prepared and studied planar Au/TiO2 thin-film model catalysts consisting of a thin mesoporous TiO2 film of 200–400 nm thickness with Au nanoparticles, with a mean particle size of ~2 nm diameter, homogeneously distributed therein. The systems were prepared by spin-coating of a mesoporous TiO2 film from solutions of ethanolic titanium tetraisopropoxide and Pluronic P123 on planar Si(100 substrates, calcination at 350 °C and subsequent Au loading by a deposition–precipitation procedure, followed by a final calcination step for catalyst activation. The structural and chemical properties of these model systems were characterized by X-ray diffraction (XRD, transmission electron microscopy (TEM, N2 adsorption, inductively coupled plasma ionization spectroscopy (ICP–OES and X-ray photoelectron spectroscopy (XPS. The catalytic properties were evaluated through the oxidation of CO as a test reaction, and reactivities were measured directly above the film with a scanning mass spectrometer. We can demonstrate that the thin-film model catalysts closely resemble dispersed Au/TiO2 supported catalysts in their characteristic structural and catalytic properties, and hence can be considered as suitable for catalytic model studies. The linear increase of the catalytic activity with film thickness indicates that transport limitations inside the Au/TiO2 film catalyst are negligible, i.e., below the detection limit.

Challenges in process integration of catalytic DC plasma synthesis of vertically aligned carbon nanofibres

International Nuclear Information System (INIS)

Melechko, Anatoli V; Pearce, Ryan C; Hensley, Dale K; Simpson, Michael L; McKnight, Timothy E

2011-01-01

The ability to synthesize free-standing, individual carbon nanofibres (CNFs) aligned perpendicularly to a substrate has enabled fabrication of a large array of devices with nanoscale functional elements, including electron field emission sources, electrochemical probes, neural interface arrays, scanning probes, gene delivery arrays and many others. This was made possible by development of a catalytic plasma process, with DC bias directing the alignment of nanofibres. Successful implementation of prototypical devices has uncovered numerous challenges in the integration of this synthesis process as one of the steps in device fabrication. This paper is dedicated to these engineering and fundamental difficulties that hinder further device development. Relatively high temperature for catalytic synthesis, electrical conductivity of the substrate to maintain DC discharge and other difficulties place restrictions on substrate material. Balancing non-catalytic carbon film deposition and substrate etching, non-uniformity of plasma due to growth of the high aspect ratio structures, plasma instabilities and other factors lead to challenges in controlling the plasma. Ultimately, controlling the atomistic processes at the catalyst nanoparticle (NP) and the behaviour of the NP is the central challenge of plasma nanosynthesis of vertically aligned CNFs.

Novel Metal Nanomaterials and Their Catalytic Applications

Directory of Open Access Journals (Sweden)

Jiaqing Wang

2015-09-01

Full Text Available In the rapidly developing areas of nanotechnology, nano-scale materials as heterogeneous catalysts in the synthesis of organic molecules have gotten more and more attention. In this review, we will summarize the synthesis of several new types of noble metal nanostructures (FePt@Cu nanowires, Pt@Fe2O3 nanowires and bimetallic Pt@Ir nanocomplexes; Pt-Au heterostructures, Au-Pt bimetallic nanocomplexes and Pt/Pd bimetallic nanodendrites; Au nanowires, CuO@Ag nanowires and a series of Pd nanocatalysts and their new catalytic applications in our group, to establish heterogeneous catalytic system in “green” environments. Further study shows that these materials have a higher catalytic activity and selectivity than previously reported nanocrystal catalysts in organic reactions, or show a superior electro-catalytic activity for the oxidation of methanol. The whole process might have a great impact to resolve the energy crisis and the environmental crisis that were caused by traditional chemical engineering. Furthermore, we hope that this article will provide a reference point for the noble metal nanomaterials’ development that leads to new opportunities in nanocatalysis.

MOTHER MK II: An advanced direct cycle high temperature gas reactor

International Nuclear Information System (INIS)

Hart, R.S.; Kendall, J.M.; Marsden, B.J.

2003-01-01

The MOTHER (MOdular Thermal HElium Reactor) power plant concepts employ high temperature gas reactors utilizing TRISO fuel, graphite moderator, and helium coolant, in combination with a direct Brayton cycle for electricity generation. The helium coolant from the reactor vessel passes through a Power Conversion Unit (PCU), which includes a turbine-generator, recuperator, precooler, intercooler and turbine-compressors, before being returned to the reactor vessel. The PCU substitutes for the reactor coolant system pumps and steam generators and most of the Balance Of Plant (BOP), including the steam turbines and condensers, employed by conventional nuclear power plants utilizing water cooled reactors. This provides a compact, efficient, and relatively simple plant configuration. The MOTHER MK I conceptual design, completed in the 1987 - 1989 time frame, was developed to economically meet the energy demands for extracting and processing heavy oil from the tar sands of western Canada. However, considerable effort was made to maximize the market potential beyond this application. Consistent with the remote and very high labour rate environment in the tar sands region, simplification of maintenance procedures and facilitation of 'change-out' in lieu of in situ repair was a design focus. MOTHER MK I had a thermal output of 288 MW and produced 120 MW electrical when operated in the electricity only production mode. An annular Prismatic reactor core was utilized, largely to minimize day-to-day operations activities. Key features of the power conversion system included two Power Conversion Units (144 MW th each), the horizontal orientation of all rotating machinery and major heat exchangers axes, high speed rotating machinery (17,030 rpm for the turbine-compressors and 10,200 rpm for the power turbine-generator), gas (helium) bearings for all rotating machinery, and solid state frequency conversion from 170 cps (at full power) to the grid frequency. Recognizing that the on

Catalytic Organic Transformations Mediated by Actinide Complexes

Directory of Open Access Journals (Sweden)

Isabell S. R. Karmel

2015-10-01

Full Text Available This review article presents the development of organoactinides and actinide coordination complexes as catalysts for homogeneous organic transformations. This chapter introduces the basic principles of actinide catalysis and deals with the historic development of actinide complexes in catalytic processes. The application of organoactinides in homogeneous catalysis is exemplified in the hydroelementation reactions, such as the hydroamination, hydrosilylation, hydroalkoxylation and hydrothiolation of alkynes. Additionally, the use of actinide coordination complexes for the catalytic polymerization of α-olefins and the ring opening polymerization of cyclic esters is presented. The last part of this review article highlights novel catalytic transformations mediated by actinide compounds and gives an outlook to the further potential of this field.

Modeling and simulation of heterogeneous catalytic processes

CERN Document Server

Dixon, Anthony

2014-01-01

Heterogeneous catalysis and mathematical modeling are essential components of the continuing search for better utilization of raw materials and energy, with reduced impact on the environment. Numerical modeling of chemical systems has progressed rapidly due to increases in computer power, and is used extensively for analysis, design and development of catalytic reactors and processes. This book presents reviews of the state-of-the-art in modeling of heterogeneous catalytic reactors and processes. Reviews by leading authorities in the respective areas Up-to-date reviews of latest techniques in modeling of catalytic processes Mix of US and European authors, as well as academic/industrial/research institute perspectives Connections between computation and experimental methods in some of the chapters.

Catalytic gasification of oil-shales

Energy Technology Data Exchange (ETDEWEB)

Lapidus, A.; Avakyan, T. [I.M. Gubkin Russian State Univ. of Oil and Gas, Moscow (Russian Federation); Strizhakova, Yu. [Samara State Univ. (Russian Federation)

2012-07-01

Nowadays, the problem of complex usage of solid fossil fuels as raw materials for obtaining of motor fuels and chemical products is becoming increasingly important. A one of possible solutions of the problem is their gasification with further processing of gaseous and liquid products. In this work we have investigated the process of thermal and catalytic gasification of Baltic and Kashpir oil-shales. We have shown that, as compared with non-catalytic process, using of nickel catalyst in the reaction increases the yield of gas, as well as hydrogen content in it, and decreases the amount of liquid products. (orig.)

Oxygen Reduction Reaction for Generating H2 O2 through a Piezo-Catalytic Process over Bismuth Oxychloride.

Science.gov (United States)

Shao, Dengkui; Zhang, Ling; Sun, Songmei; Wang, Wenzhong

2018-02-09

Oxygen reduction reaction (ORR) for generating H 2 O 2 through green pathways have gained much attention in recent years. Herein, we introduce a piezo-catalytic approach to obtain H 2 O 2 over bismuth oxychloride (BiOCl) through an ORR pathway. The piezoelectric response of BiOCl was directly characterized by piezoresponse force microscopy (PFM). The BiOCl exhibits efficient catalytic performance for generating H 2 O 2 (28 μmol h -1 ) only from O 2 and H 2 O, which is above the average level of H 2 O 2 produced by solar-to-chemical processes. A piezo-catalytic mechanism was proposed: with ultrasonic waves, an alternating electric field will be generated over BiOCl, which can drive charge carriers (electrons) to interact with O 2 and H 2 O, then to form H 2 O 2 . © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Direct observation of doping incorporation pathways in self-catalytic GaMnAs nanowires

Energy Technology Data Exchange (ETDEWEB)

Kasama, T., E-mail: tk@cen.dtu.dk; Yazdi, S. [Center for Electron Nanoscopy, Technical University of Denmark, DK-2800 Kongens Lyngby (Denmark); Thuvander, M. [Department of Applied Physics, Chalmers University of Technology, SE-41296 Gothenburg (Sweden); Siusys, A. [Institute of Physics, Polish Academy of Sciences, al. Lotników 32/46, PL-02-668 Warszawa (Poland); Gontard, L. C. [Instituto de Ciencia de Materiales de Sevilla (CSIC-US), C/Américo Vespucio 49, 41092 Seville (Spain); Kovács, A.; Duchamp, M.; Dunin-Borkowski, R. E. [Ernst Ruska-Centre for Microscopy and Spectroscopy with Electrons and Peter Grünberg Institute, Forschungszentrum Jülich, D-52425 Jülich (Germany); Gustafsson, A. [Solid State Physics and the Nanometer Structure Consortium, Lund University, P.O. Box 118, SE-221 00 Lund (Sweden); Sadowski, J. [Institute of Physics, Polish Academy of Sciences, al. Lotników 32/46, PL-02-668 Warszawa (Poland); MAX-IV Laboratory, Lund University, P.O. Box 118, SE-221 00 Lund (Sweden)

2015-08-07

Doping mechanisms of Mn in GaAs nanowires (NWs) that have been grown self-catalytically at 600 °C by molecular beam epitaxy (MBE) are investigated using advanced electron microscopy techniques and atom probe tomography. Mn is found to be incorporated primarily in the form of non-magnetic tetragonal Ga{sub 0.82}Mn{sub 0.18} nanocrystals in Ga catalyst droplets at the ends of the NWs, while trace amounts of Mn (22 ± 4 at. ppm) are also distributed randomly in the NW bodies without forming clusters or precipitates. The nanocrystals are likely to form after switching off the reaction in the MBE chamber, since they are partially embedded in neck regions of the NWs. The Ga{sub 0.82}Mn{sub 0.18} nanocrystals and the low Mn concentration in the NW bodies are insufficient to induce a ferromagnetic phase transition, suggesting that it is difficult to have high Mn contents in GaAs even in 1-D NW growth via the vapor-liquid-solid process.

Spectromicroscopy of catalytic relevant processes with sub-micron resolution

International Nuclear Information System (INIS)

Guenther, S.; Esch, F.; Gregoratti, L.; Marsi, M.; Kiskinova, M.; Schubert, U. A.; Grotz, P.; Knoezinger, H.; Taglauer, E.; Schuetz, E.; Schaak, A.; Imbihl, R.

2000-01-01

The capabilities of the Scanning Photo Electron Microscope (SPEM) at ELETTRA as a unique probing tool in the field of catalysis and surface science are illustrated presenting results of two recent investigations. The lateral resolution and the high surface sensitivity of the SPEM has enabled imaging the initial steps of the spreading processes of MoO 3 crystals on an alumina support surface, a model system of a catalyst used in petrochemistry. In the second study the local adsorbate coverage inside a pulse of a chemical wave occurring in the catalytic NO+H 2 reaction on a Rh(110) single crystal surface has been determined. The microscope was used to monitor the sample surface in situ during the reaction and thus characterizing a temporal and spatial inhomogeneous system. The so-called excitation cycle of the pulse formation has been verified and the adsorbate gradient inside a chemical wave was measured

Direct liquefaction of wood through solvolysis and catalytic hydrodeoxygenation: an engineering assessment

Energy Technology Data Exchange (ETDEWEB)

Moffat, J.M.; Overend, J.P.

1985-01-01

Liquefaction of wood to produce fuel and chemical intermediates has been intensively studied over the last decade. The results of Canadian research into process feasibility are presented on the basis of two studies, the first in 1980 utilizing data of the mid-70s and the other on the basis of research conducted up to 1982. The earlier study was for a single reactor concept in which catalyst, wood and hydrogen were reacted to produce a proto-oil, while the later study embodies a two-stage concept involving dissolution of the polymer matrix followed by fractionation and catalytic upgrading using hydrodeoxygenation. Increased knowledge of the characteristics of the first stage products show that there are many component mixtures containing between 10 and 20% oxygen. Most of the oxygen is in aromatic phenol-type structures with some ether linkages, and low severity processes to deoxygenate the product while increasing the hydrogen to carbon ratio are called for. The economic prospects for a two-stage process are described on the basis of a hydrocarbon process proposed by HRI International for Kraft process lignin. These show that a mix of BTX products and fuel oil could generate a profitable rate of return. 62 references.

Electrooxidation of borohydride on platinum and gold electrodes: implications for direct borohydride fuel cells

Energy Technology Data Exchange (ETDEWEB)

Gyenge, E. [University of British Columbia, Vancouver (Canada). Dept. of Chemical and Biological Engineering

2004-03-01

The electrochemical oxidation of BH{sub 4}{sup -} in 2M NaOH on Pt and Au (i.e. catalytic and non-catalytic electrodes, respectively, for BH{sub 4}{sup -} hydrolysis accompanied by H{sub 2} evolution) has been studied by cyclic voltammetry, chrono-techniques (i.e., potentiometry, amperometry, coulometry) and electrochemical impedance spectroscopy. In the case of Pt the cyclic voltammetry behaviour of BH{sub 4}{sup -} is influenced by both, the catalytic hydrolysis of BH{sub 4}{sup -} yielding H{sub 2} followed by electrooxidation of the latter at peak potentials between -0.7 and -0.9 V versus Ag/AgCl, KCl{sub std} and direct oxidation of BH{sub 4}{sup -} at more positive potentials, i.e., between -0.15 and -0.05 V. Thiourea (TU, 1.5 x 10{sup -3} M) was an effective inhibitor of the catalytic hydrolysis associated with BH{sub 4}{sup -} electrooxidation on Pt. Therefore, in the presence of TU, only the direct oxidation of BH{sub 4}{sup -} has been detected, with peak potentials between -0.2 and 0 V. It is proposed that TU could improve the BH{sub 4}{sup -} utilization efficiency and the coulombic efficiency of direct borohydride fuel cells using catalytic anodes. The electrooxidation of BH{sub 4}{sup -} on Pt/TU is an overall four-electron process, instead of the maximum eight electrons reported for Au, and it is affected by adsorbed species such as BH{sub 4}{sup -} (fractional surface coverage {approx}0.3), TU and possibly reaction intermediates. (author)

Nano-Engineered Catalysts for Direct Methanol Fuel Cells

Science.gov (United States)

Myung, Nosang; Narayanan, Sekharipuram; Wiberg, Dean

2008-01-01

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

Kinetic catalytic studies of scorpion's hemocyanin

International Nuclear Information System (INIS)

Queinnec, E.; Vuillaume, M.; Gardes-Albert, M.; Ferradini, C.; Ducancel, F.

1991-01-01

Hemocyanins are copper proteins which function as oxygen carriers in the haemolymph of Molluscs and Arthropods. They possess enzymatic properties: peroxidatic and catalatic activities, although they have neither iron nor porphyrin ring at the active site. The kinetics of the catalytic reaction is described. The reaction of superoxide anion with hemocyanin has been studied using pulse radiolysis at pH 9. The catalytic rate constant is 3.5 X 10 7 mol -1 .l.s -1 [fr

Detection of Intracellular Reduced (Catalytically Active) SHP-1 and Analyses of Catalytically Inactive SHP-1 after Oxidation by Pervanadate or H2O2.

Science.gov (United States)

Choi, Seeyoung; Love, Paul E

2018-01-05

Oxidative inactivation of cysteine-dependent Protein Tyrosine Phosphatases (PTPs) by cellular reactive oxygen species (ROS) plays a critical role in regulating signal transduction in multiple cell types. The phosphatase activity of most PTPs depends upon a 'signature' cysteine residue within the catalytic domain that is maintained in the de-protonated state at physiological pH rendering it susceptible to ROS-mediated oxidation. Direct and indirect techniques for detection of PTP oxidation have been developed (Karisch and Neel, 2013). To detect catalytically active PTPs, cell lysates are treated with iodoacetyl-polyethylene glycol-biotin (IAP-biotin), which irreversibly binds to reduced (S - ) cysteine thiols. Irreversible oxidation of SHP-1 after treatment of cells with pervanadate or H 2 O 2 is detected with antibodies specific for the sulfonic acid (SO 3 H) form of the conserved active site cysteine of PTPs. In this protocol, we describe a method for the detection of the reduced (S - ; active) or irreversibly oxidized (SO 3 H; inactive) form of the hematopoietic PTP SHP-1 in thymocytes, although this method is applicable to any cysteine-dependent PTP in any cell type.

Advanced orient cycle, for strategic separation, transmutation and utilization of nuclides in the nuclear fuel cycle

International Nuclear Information System (INIS)

Ozawa, M.; Fujita, R.; Koyama, S.; Suzuki, T.; Fujii, Y.

2007-01-01

Electrolytic extraction (EE) method has been studied as a vital separation tool for new reprocessing process to realize transmutation and utilization of the specific fission products including LLFP * (e.g., Tc * , Ru, Rh, Pd * , Se * and Te * , etc) in the spent nuclear fuel. In an employed EE process, Pd 2 + cation itself would not only be easily (>99%) deposited from various nitric acid solutions, but enhance also the deposition of co-existing RuNO 3 + and ReO 4 - by acting as a catalyst (as Pd a datom). Such a catalytic electrolytic extraction (i.e., CEE) method was also applicable in the case of 9 9TcO 4 - deposition as well. Addition of Pd 2 + caused either to change the dendritic metal deposition form or to improve electrochemical property of deposits. The RMFP deposit, especially quaternary-, Pd-Ru-Rh-Re, deposits on the Pt electrode obtained by the CEE method were rather spherical in shape, seemed to be electrochemically agglomerated by nano particles. The deposits were stable and showed electrochemically nobler initial hydrogen evolution potential (φ H int.). Also in the given potential of -1.25 V (vs. Ag/AgCl), the quaternary-, Pd-Ru-Rh-Re, deposit Pt electrode suggested the highest cathodic current corresponding to the hydrogen generation reaction. Namely, those catalytic activities were ca. twice superior to that of the Pt electrode in alkaline solution. The sea water is a possible resource for hydrogen production in future. In the course of sea water electrolysis, disturbance due to Ca(OH) 2 and Mg(OH) 2 precipitation was inevitable, but the cathodic current of the quaternary deposit of RMFP was the highest, the same as to that of Pt electrode in the alkaline water. Therefore, RMFP has a potential to alternate with Pt catalyst. The electrochemical property of Re and 9 9Tc, as for alternative element to Re, are under investigation with a special interest of this direction of utilization. The renovative reprocessing flow sheet by tertiary pyridine resin

Tunable preparation of ruthenium nanoparticles with superior size-dependent catalytic hydrogenation properties

Energy Technology Data Exchange (ETDEWEB)

Zhao, Yuan; Luo, Yaodong; Yang, Xuan; Yang, Yaxin; Song, Qijun, E-mail: qsong@jiangnan.edu.cn

2017-06-15

Highlights: • A facile and efficient strategy is firstly developed for the synthesis of Ru NPs. • Ru NPs are stable and uniform with the controllable sizes from 2.6 to 51.5 nm. • Ru NPs exhibit size-dependent and superior catalytic hydrogenation activity. - Abstract: Ruthenium (Ru) featured with an unusual catalytic behavior is of great significance in several heterogeneous and electro-catalytic reactions. The preparation of tractable Ru nanocatalysts and the building of highly active catalytic system at ambient temperature remains a grand challenge. Herein, a facile strategy is developed for the controllable preparation of Ru nanoparticles (NPs) with the sizes ranging from 2.6 to 51.5 nm. Ru NPs show superior size-dependent catalytic performance with the best kinetic rate constant as high as −1.52 min{sup −1}, which could far surpass the other traditional noble metals. Ru NPs exert exceedingly efficient low-temperature catalytic activity and good recyclability in the catalytic reduction of nitroaromatic compounds (NACs) and azo dyes. The developed catalytic system provides a distinguishing insight for the artificial preparation of Ru NPs with desired sizes, and allows for the development of rational design rules for exploring catalysts with superior catalytic performances, potentially broadening the applications of metallic NP-enabled catalytic analysis.

Orion EFT-1 Catalytic Tile Experiment Overview and Flight Measurements

Science.gov (United States)

Salazar, Giovanni; Amar, Adam; Hyatt, Andrew; Rezin, Marc D.

2016-01-01

This paper describes the design and results of a surface catalysis flight experiment flown on the Orion Multipurpose Crew Vehicle during Exploration Flight Test 1 (EFT1). Similar to previous Space Shuttle catalytic tile experiments, the present test consisted of a highly catalytic coating applied to an instrumented TPS tile. However, the present catalytic tile experiment contained significantly more instrumentation in order to better resolve the heating overshoot caused by the change in surface catalytic efficiency at the interface between two distinct materials. In addition to collecting data with unprecedented spatial resolution of the "overshoot" phenomenon, the experiment was also designed to prove if such a catalytic overshoot would be seen in turbulent flow in high enthalpy regimes. A detailed discussion of the results obtained during EFT1 is presented, as well as the challenges associated with data interpretation of this experiment. Results of material testing carried out in support of this flight experiment are also shown. Finally, an inverse heat conduction technique is employed to reconstruct the flight environments at locations upstream and along the catalytic coating. The data and analysis presented in this work will greatly contribute to our understanding of the catalytic "overshoot" phenomenon, and have a significant impact on the design of future spacecraft.

Future directions and cycles for electricity production from geothermal resources

International Nuclear Information System (INIS)

Michaelides, Efstathios E.

2016-01-01

Graphical abstract: 25% more power may be produced using binary-flashing geothermal cycles. - Highlights: • Power from geothermal power plants is continuously available and “dispatchable.” • The next generation of geothermal will include more binary plants. • Lower temperature geothermal resources will be utilized in the future. • Dry rock resources may produce a high fraction of electricity in several countries. - Abstract: Geothermal power production is economically competitive and capable to produce a high percentage of the electric power demand in several countries. The currently operating geothermal power plants utilize water from an aquifer at relatively higher temperatures and produce power using dry steam, flashing or binary cycles. A glance at the map of the global geothermal resources proves that there is a multitude of sites, where the aquifer temperature is lower. There are also many geothermal resources where a high geothermal gradient exists in the absence of an aquifer. It becomes apparent that the next generation of geothermal power plants will utilize more of the lower-temperature aquifer resources or the dry resources. For such power plants to be economically competitive, modified or new cycles with higher efficiencies must be used. This paper presents two methods to increase the efficiency of the currently used geothermal cycles. The first uses a binary-flashing system to reduce the overall entropy production, thus, producing more electric power from the resource. The second describes a heat extraction system to be used with dry hot-rock resources.

Networks of high mutual information define the structural proximity of catalytic sites: implications for catalytic residue identification.

Directory of Open Access Journals (Sweden)

Cristina Marino Buslje

Full Text Available Identification of catalytic residues (CR is essential for the characterization of enzyme function. CR are, in general, conserved and located in the functional site of a protein in order to attain their function. However, many non-catalytic residues are highly conserved and not all CR are conserved throughout a given protein family making identification of CR a challenging task. Here, we put forward the hypothesis that CR carry a particular signature defined by networks of close proximity residues with high mutual information (MI, and that this signature can be applied to distinguish functional from other non-functional conserved residues. Using a data set of 434 Pfam families included in the catalytic site atlas (CSA database, we tested this hypothesis and demonstrated that MI can complement amino acid conservation scores to detect CR. The Kullback-Leibler (KL conservation measurement was shown to significantly outperform both the Shannon entropy and maximal frequency measurements. Residues in the proximity of catalytic sites were shown to be rich in shared MI. A structural proximity MI average score (termed pMI was demonstrated to be a strong predictor for CR, thus confirming the proposed hypothesis. A structural proximity conservation average score (termed pC was also calculated and demonstrated to carry distinct information from pMI. A catalytic likeliness score (Cls, combining the KL, pC and pMI measures, was shown to lead to significantly improved prediction accuracy. At a specificity of 0.90, the Cls method was found to have a sensitivity of 0.816. In summary, we demonstrate that networks of residues with high MI provide a distinct signature on CR and propose that such a signature should be present in other classes of functional residues where the requirement to maintain a particular function places limitations on the diversification of the structural environment along the course of evolution.

Networks of high mutual information define the structural proximity of catalytic sites: implications for catalytic residue identification.

Science.gov (United States)

Marino Buslje, Cristina; Teppa, Elin; Di Doménico, Tomas; Delfino, José María; Nielsen, Morten

2010-11-04

Identification of catalytic residues (CR) is essential for the characterization of enzyme function. CR are, in general, conserved and located in the functional site of a protein in order to attain their function. However, many non-catalytic residues are highly conserved and not all CR are conserved throughout a given protein family making identification of CR a challenging task. Here, we put forward the hypothesis that CR carry a particular signature defined by networks of close proximity residues with high mutual information (MI), and that this signature can be applied to distinguish functional from other non-functional conserved residues. Using a data set of 434 Pfam families included in the catalytic site atlas (CSA) database, we tested this hypothesis and demonstrated that MI can complement amino acid conservation scores to detect CR. The Kullback-Leibler (KL) conservation measurement was shown to significantly outperform both the Shannon entropy and maximal frequency measurements. Residues in the proximity of catalytic sites were shown to be rich in shared MI. A structural proximity MI average score (termed pMI) was demonstrated to be a strong predictor for CR, thus confirming the proposed hypothesis. A structural proximity conservation average score (termed pC) was also calculated and demonstrated to carry distinct information from pMI. A catalytic likeliness score (Cls), combining the KL, pC and pMI measures, was shown to lead to significantly improved prediction accuracy. At a specificity of 0.90, the Cls method was found to have a sensitivity of 0.816. In summary, we demonstrate that networks of residues with high MI provide a distinct signature on CR and propose that such a signature should be present in other classes of functional residues where the requirement to maintain a particular function places limitations on the diversification of the structural environment along the course of evolution.

Heterogeneous catalytic degradation of polyacrylamide solution | Hu ...

African Journals Online (AJOL)

Modified with trace metal elements, the catalytic activity of Fe2O3/Al2O3 could be changed greatly. Among various trace metal elements, Fe2O3/Al2O3 catalysts modified with Co and Cu showed great increase on catalytic activity. International Journal of Engineering, Science and Technology, Vol. 2, No. 7, 2010, pp. 110- ...

Catalytic formal [2+2+1] synthesis of pyrroles from alkynes and diazenes via Ti(II)/Ti(IV) redox catalysis.

Science.gov (United States)

Gilbert, Zachary W; Hue, Ryan J; Tonks, Ian A

2016-01-01

Pyrroles are structurally important heterocycles. However, the synthesis of polysubstituted pyrroles is often challenging. Here, we report a multicomponent, Ti-catalysed formal [2+2+1] reaction of alkynes and diazenes for the oxidative synthesis of penta- and trisubstituted pyrroles: a nitrenoid analogue to classical Pauson-Khand-type syntheses of cyclopentenones. Given the scarcity of early transition-metal redox catalysis, preliminary mechanistic studies are presented. Initial stoichiometric and kinetic studies indicate that the mechanism of this reaction proceeds through a formally Ti(II)/Ti(IV) redox catalytic cycle, in which an azatitanacyclobutene intermediate, resulting from [2+2] alkyne + Ti imido coupling, undergoes a second alkyne insertion followed by reductive elimination to yield pyrrole and a Ti(II) species. The key component for catalytic turnover is the reoxidation of the Ti(II) species to a Ti(IV) imido via the disproportionation of an η(2)-diazene-Ti(II) complex.

High selectivity and stability of Mg-doped Al-MCM-41 for in-situ catalytic upgrading fast pyrolysis bio-oil

International Nuclear Information System (INIS)

Karnjanakom, Surachai; Suriya-umporn, Thanyamai; Bayu, Asep; Kongparakul, Suwadee; Samart, Chanatip; Fushimi, Chihiro; Abudula, Abuliti; Guan, Guoqing

2017-01-01

Highlights: • Mg-doped Al-MCM-41 was developed for in-situ catalytic upgrading of bio-oils. • Mg/Al-MCM-41 exhibited high selectivity to aromatic hydrocarbons. • The ratio of produced hydrocarbon reached up to 80% in upgraded bio-oil. • 1 wt.% Mg/Al-MCM-41 showed the highest catalytic activity. • Mg/Al-MCM-41 had stable reusability due to its coking inhabitation ability. - Abstract: In-situ catalytic upgrading of bio-oils derived from the fast pyrolysis of cellulose, lignin or sunflower stalk over Mg-doped Al-MCM-41 was investigated in details. It is found that Mg species with doping amounts ranged between 0.25 and 10 wt.% was well dispersed on Al-MCM-41, and that doping Mg on Al-MCM-41 effectively adjusted the acidity and basicity of the catalysts, resulting in significant improvement of bio-oil quality. Mg/Al-MCM-41 exhibited high selective conversion of bio-oils derived from cellulose, lignin or sunflower stalk to high value-added aromatic hydrocarbons via catalytic cracking, deoxygenation and aromatization. In the upgraded bio-oil, the relative total hydrocarbon amount reached up to approximately ≥80%, which consisted of aromatic hydrocarbon approximately 76% and aliphatic hydrocarbon approximately 4% for all feedstocks. The selectivity to the monocyclic aromatic hydrocarbons (MAHs) such as benzene, toluene and xylenes (BTXs) increased while the coke formed on the catalyst decreased with the increase in Mg doping amount. 1 wt.% Mg/Al-MCM-41 resulted in the highest relative total hydrocarbon amount in the upgraded bio-oil at lower catalytic deoxygenation temperature, and showed stable reusability for at least 5 cycles. It is expected that Mg/Al-MCM-41 can be widely applied for bio-oil upgrading in a practical process.

SHORT COMMUNICATION CATALYTIC KINETIC ...

African Journals Online (AJOL)

IV) catalyzes the discoloring reaction of DBS-arsenazo oxidized by potassium bromate, a new catalytic kinetic spectrophotometric method for the determination of trace titanium (IV) was developed. The linear range of the determination of ...

Catalytic Kinetic Resolution of Biaryl Compounds.

Science.gov (United States)

Ma, Gaoyuan; Sibi, Mukund P

2015-08-10

Biaryl compounds with axial chirality are very common in synthetic chemistry, especially in catalysis. Axially chiral biaryls are important due to their biological activities and extensive applications in asymmetric catalysis. Thus the development of efficient enantioselective methods for their synthesis has attracted considerable attention. This Minireview discusses the progress made in catalytic kinetic resolution of biaryl compounds and chronicles significant advances made recently in catalytic kinetic resolution of biaryl scaffolds. © 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.

synthesis, characterization, electrical and catalytic studies of some

African Journals Online (AJOL)

B. S. Chandravanshi

catalytic activity of the VO(IV) and Mn(III) complexes have been tested in the epoxidation reaction of styrene ... Vanadyl sulfate pentahydrate, chromium chloride hexahydrate, anhydrous ferric ..... The catalytic oxidation of styrene gives the products styrene oxide, benzaldehyde, benzoic acid, ... bond via a radical mechanism.

Towards Prebiotic Catalytic Amyloids Using High Throughput Screening.

Directory of Open Access Journals (Sweden)

Michael P Friedmann

Full Text Available Enzymes are capable of directing complex stereospecific transformations and of accelerating reaction rates many orders of magnitude. As even the simplest known enzymes comprise thousands of atoms, the question arises as to how such exquisite catalysts evolved. A logical predecessor would be shorter peptides, but they lack the defined structure and size that are apparently necessary for enzyme functions. However, some very short peptides are able to assemble into amyloids, thereby forming a well-defined tertiary structure called the cross-β-sheet, which bestows unique properties upon the peptides. We have hypothesized that amyloids could have been the catalytically active precursor to modern enzymes. To test this hypothesis, we designed an amyloid peptide library that could be screened for catalytic activity. Our approach, amenable to high-throughput methodologies, allowed us to find several peptides and peptide mixtures that form amyloids with esterase activity. These results indicate that amyloids, with their stability in a wide range of conditions and their potential as catalysts with low sequence specificity, would indeed be fitting precursors to modern enzymes. Furthermore, our approach can be efficiently expanded upon in library size, screening conditions, and target activity to yield novel amyloid catalysts with potential applications in aqueous-organic mixtures, at high temperature and in other extreme conditions that could be advantageous for industrial applications.

Three dimensional carbon-bubble foams with hierarchical pores for ultra-long cycling life supercapacitors.

Science.gov (United States)

Wang, Bowen; Zhang, Weigang; Wang, Lei; Wei, Jiake; Bai, Xuedong; Liu, Jingyue; Zhang, Guanhua; Duan, Huigao

2018-07-06

Design and synthesis of integrated, interconnected porous structures are critical to the development of high-performance supercapacitors. We develop a novel and facile synthesis technic to construct three-dimensional carbon-bubble foams with hierarchical pores geometry. The carbon-bubble foams are fabricated by conformally coating, via catalytic decomposition of ethanol, a layer of carbon coating onto the surfaces of pre-formed ZnO foams and then the removal of the ZnO template by a reduction-evaporation process. Both the wall thickness and the pore size can be well tuned by adjusting the catalytic decomposition time and temperature. The as-synthesized carbon-bubble foams electrode retains 90.3% of the initial capacitance even after 70 000 continuous cycles under a high current density of 20 A g -1 , demonstrating excellent long-time electrochemical and cycling stability. The symmetric device displays rate capability retention of 81.8% with the current density increasing from 0.4 to 20 A g -1 . These achieved electrochemical performances originate from the unique structural design of the carbon-bubble foams, which provide not only abundant transport channels for electron and ion but also high active surface area accessible by the electrolyte ions.

Efficient Catalytic Conversion of Ethanol to 1-Butanol via the Guerbet Reaction over Copper- and Nickel-Doped Porous

NARCIS (Netherlands)

Sun, Zhuohua; Vasconcelos, Anais Couto; Bottari, Giovanni; Stuart, Marc C. A.; Bonura, Giuseppe; Cannilla, Catia; Frusteri, Francesco; Barta, Katalin

The direct conversion of ethanol to higher value 1-butanol is a catalytic transformation of great interest in light of the expected wide availability of bioethanol originating from the fermentation of renewable resources. In this contribution we describe several novel compositions of porous metal

Transient simulation of a catalytic converter for a dual fuel engine

Energy Technology Data Exchange (ETDEWEB)

Liu, B.; Checkel, D. [Alberta Univ., Dept. of Mechanical Enginering, Edmonton, AB (Canada); Hayes, R. E. [Alberta Univ., Department of Chemical and Material Engineering, Edmonton, AB (Canada); Zheng, M.; Mirosh, E. [Alternative Fuel Systems Inc., Calgary, AB (Canada)

2000-06-01

A catalytic converter of a ceramic monolith honeycomb substrate, coated with a washcoat of catalyst and attached to a natural gas/diesel dual fuel engine was simulated and studied experimentally. The paper describes the application of one-dimensional finite element model for the transient and steady state operation. Laminar flow was approximated using a dispersed plug flow model, and chemical kinetics were simulated using LHHW (Langmuir/ Hinshelwood/ Hougan/ Watson) type expressions. Simulation results were compared with experimental results for heating and cooling cycles which resulted from speed and load changes on the engine. The comparison showed a maximum difference between the two sets of emission levels of about 10 per cent, showing that the one-dimensional model is acceptable model for this dual fuel engine converter combination. 50 refs., 3 tabs., 13 figs.

In situ synthesis and catalytic application of reduced graphene oxide supported cobalt nanowires

Science.gov (United States)

Xu, Zhiqiang; Long, Qin; Deng, Yi; Liao, Li

2018-05-01

Controlled synthesis of magnetic nanocomposite with outstanding catalytic performances is a promising strategy in catalyst industry. We proposed a novel concept for fabrication of reduced graphene oxide-supported cobalt nanowires (RGO/Co-NWs) nanocomposite as high-efficient magnetic catalyst. Unlike the majority of experiments necessitating harsh synthesis conditions such as high-pressure, high-temperature and expensive template, here the RGO/Co-NWs were successfully prepared in aqueous solution under mild conditions with the assistance of external magnetic field. The synthetic process was facile and external magnetic force was adopted to induce the unidirectional self-assembly of cobalt crystals on graphene oxide to form RGO/Co-NWs. The possible formation mechanism laid on the fact that the dipole magnetic moments of the nanoparticles were aligned along the magnetic induction lines with the external magnetic field direction resulting in the formation of nanowires elongating in the direction of the magnetization axis. Simultaneously, a series of controlled reactions were conducted to illuminate the effect of graphene oxide, external magnetic field and PVP on the morphology and size of RGO/Co-NWs in the present approach. More importantly, the nanocomposite exhibited a high catalytic performance towards ammonia borane. Hence the novel nanocomposite holds a great potential for technological applications such as catalyst industry.

CATALYTIC KINETIC SPECTROPHOTOMETRIC DETERMINATION ...

African Journals Online (AJOL)

Preferred Customer

acetylchlorophosphonazo(CPApA) by hydrogen peroxide in 0.10 M phosphoric acid. A novel catalytic kinetic-spectrophotometric method is proposed for the determination of copper based on this principle. Copper(II) can be determined spectrophotometrically ...

On Acyclicity of Games with Cycles

DEFF Research Database (Denmark)

Andersson, Daniel; Gurvich, Vladimir; Hansen, Thomas Dueholm

2009-01-01

We study restricted improvement cycles (ri-cycles) in finite positional n-person games with perfect information modeled by directed graphs (digraphs) that may contain cycles. We obtain criteria of restricted improvement acyclicity (ri-acyclicity) in two cases: for n = 2 and for acyclic digraphs. We...

Production of hydrogen from bio-ethanol in catalytic membrane reactor

International Nuclear Information System (INIS)

Gernot, E.; Aupretre, F.; Deschamps, A.; Etievant, C.; Epron, F.; Marecot, P.; Duprez, D.

2006-01-01

Production of hydrogen from renewable energy sources offers a great potential for CO 2 emission reduction, responsible for global warming. Among renewable energies, liquid biofuels are very convenient hydrogen carriers for decentralized applications such as micro-cogeneration and transports. Ethanol, produced from sugar plants and cereals, allows a reduction of more than 60% of CO 2 emissions in comparison to gasoline. BIOSTAR is an R and D project, co-funded by the French Agency for Environment and Energy Management (ADEME) which aims at developing an efficient source of hydrogen from bio-ethanol, suitable for proton exchange membrane fuel cell systems. The objectives are to obtain, through catalytic process at medium temperature range, an efficient conversion of bio-ethanol into pure hydrogen directly usable for PEMFC. CETH has developed a catalytic membrane reformer (CMR), based on a patented technology, integrating a steam reforming catalyst as well as a combustion catalyst. Both catalysts have been developed and optimized for membrane reactor in partnership with the University of Poitiers. The composite metallic membrane developed by CETH allows hydrogen extraction near the hydrogen production sites, which enhances both efficiency and compactness. (authors)

Bimetallic Nanoparticles in Alternative Solvents for Catalytic Purposes

Directory of Open Access Journals (Sweden)

Trung Dang-Bao

2017-07-01

Full Text Available Bimetallic nanoparticles represent attractive catalytic systems thanks to the synergy between both partners at the atomic level, mainly induced by electronic effects which in turn are associated with the corresponding structures (alloy, core-shell, hetero-dimer. This type of engineered material can trigger changes in the kinetics of catalyzed processes by variations on the electrophilicity/nucleophilicity of the metal centers involved and also promote cooperative effects to foster organic transformations, including multi-component and multi-step processes. Solvents become a crucial factor in the conception of catalytic processes, not only due to their environmental impact, but also because they can preserve the bimetallic structure during the catalytic reaction and therefore increase the catalyst life-time. In this frame, the present review focuses on the recent works described in the literature concerning the synthesis of bimetallic nanoparticles in non-conventional solvents, i.e., other than common volatile compounds, for catalytic applications.

Simulation of Cycle-to-Cycle Variation in Dual-Fuel Engines

KAUST Repository

Jaasim, Mohammed

2017-03-13

Standard practices of internal combustion (IC) engine experiments are to conduct the measurements of quantities averaged over a large number of cycles. Depending on the operating conditions, the cycle-to-cycle variation (CCV) of quantities, such as the indicated mean effective pressure (IMEP) are observed at different levels. Accurate prediction of CCV in IC engines is an important but challenging task. Computational fluid dynamics (CFD) simulations using high performance computing (HPC) can be used effectively to visualize such 3D spatial distributions. In the present study, a dual fuel large engine is considered, with natural gas injected into the manifold accompanied with direct injection of diesel pilot fuel to trigger ignition. Multiple engine cycles in 3D are simulated in series as in the experiments to investigate the potential of HPC based high fidelity simulations to accurately capture the cycle to cycle variation in dual fuel engines. Open cycle simulations are conducted to predict the combined effect of the stratification of fuel-air mixture, temperature and turbulence on the CCV of pressure. The predicted coefficient of variation (COV) of pressure compared to the results from closed cycle simulations and the experiments.

Catalytic and thermal cracking processes of waste cooking oil for bio-gasoline synthesis

Science.gov (United States)

Dewanto, Muhammad Andry Rizki; Januartrika, Aulia Azka; Dewajani, Heny; Budiman, Arief

2017-03-01

Non-renewable energy resources such as fossil fuels, and coal were depleted as the increase of global energy demand. Moreover, environmental aspect becomes a major concern which recommends people to utilize bio-based resources. Waste cooking oil is one of the economical sources for biofuel production and become the most used raw material for biodiesel production. However, the products formed during frying, can affect the trans-esterification reaction and the biodiesel properties. Therefore, it needs to convert low-quality cooking oil directly into biofuel by both thermal and catalytic cracking processes. Thermal and catalytic cracking sometimes are regarded as prospective bio-energy conversion processes. This research was carried out in the packed bed reactor equipped with 2 stages preheater with temperature of reactor was variated in the range of 450-550°C. At the same temperature, catalytic cracking had been involved in this experiment, using activated ZSM-5 catalyst with 1 cm in length. The organic liquid product was recovered by three stages of double pipe condensers. The composition of cracking products were analyzed using GC-MS instrument and the caloric contents were analyzed using Bomb calorimeter. The results reveal that ZSM-5 was highly selective toward aromatic and long aliphatic compounds formation. The percentage recovery of organic liquid product from the cracking process varies start from 8.31% and the optimal results was 54.08%. The highest heating value of liquid product was resulted from catalytic cracking process at temperature of 450°C with value of 10880.48 cal/gr and the highest product yield with 54.08% recovery was achieved from thermal cracking process with temperature of 450°C.

Improved thermostability and enzyme activity of a recombinant phyA mutant phytase from Aspergillus niger N25 by directed evolution and site-directed mutagenesis.

Science.gov (United States)

Tang, Zizhong; Jin, Weiqiong; Sun, Rong; Liao, Yan; Zhen, Tianrun; Chen, Hui; Wu, Qi; Gou, Lin; Li, Chenlei

2018-01-01

We previously constructed three recombinant phyA mutant strains (PP-NP m -8, PP-NP ep -6A and I44E/T252R-PhyA), showing improved catalytic efficiency or thermostability of Aspergillus niger N25 phytase, by error-prone PCR or site-directed mutagenesis. In this study, directed evolution and site-directed mutagenesis were further applied to improve the modified phytase properties. After one-round error-prone PCR for phytase gene of PP-NP ep -6A, a single transformant, T195L/Q368E/F376Y, was obtained with the significant improvements in catalytic efficiency and thermostability. The phytase gene of T195L/Q368E/F376Y, combined with the previous mutant phytase genes of PP-NP ep -6A, PP-NP m -8 and I44E/T252R-PhyA, was then sequentially modified by DNA shuffling. Three genetically engineered strains with desirable properties were then obtained, namedQ172R, Q172R/K432R andQ368E/K432R. Among them, Q172R/K432R showed the highest thermostability with the longest half-life and the greatest remaining phytase activity after heat treatment, while Q368E/K432R showed the highest catalytic activity. Five substitutions (Q172R, T195L, Q368E, F376Y, K432R) identified from random mutagenesis were added sequentially to the phytase gene of PP-NP ep -6A to investigate how the mutant sites influence the properties of phytase. Characterization and structural analysis demonstrated that these mutations could produce cumulative or synergistic improvements in thermostability or catalytic efficiency of phytase. Copyright © 2017 Elsevier Inc. All rights reserved.

Catalytic methanol dissociation

International Nuclear Information System (INIS)

Alcinikov, Y.; Fainberg, V.; Garbar, A.; Gutman, M.; Hetsroni, G.; Shindler, Y.; Tatrtakovsky, L.; Zvirin, Y.

1998-01-01

Results of the methanol dissociation study on copper/potassium catalyst with alumina support at various temperatures are presented. The following gaseous and liquid products at. The catalytic methanol dissociation is obtained: hydrogen, carbon monoxide, carbon dioxide, methane, and dimethyl ether. Formation rates of these products are discussed. Activation energies of corresponding reactions are calculated

Review of the direct thermochemical conversion of lignocellulosic biomass for liquid fuels

Directory of Open Access Journals (Sweden)

Jianchun JIANG,Junming XU,Zhanqian SONG

2015-03-01

Full Text Available Increased demand for liquid transportation fuels, environmental concerns and depletion of petroleum resources requires the development of efficient conversion technologies for production of second-generation biofuels from non-food resources. Thermochemical approaches hold great potential for conversion of lignocellulosic biomass into liquid fuels. Direct thermochemical processes convert biomass into liquid fuels in one step using heat and catalysts and have many advantages over indirect and biological processes, such as greater feedstock flexibility, integrated conversion of whole biomass, and lower operation costs. Several direct thermochemical processes are employed in the production of liquid biofuels depending on the nature of the feedstock properties: such as fast pyrolysis/liquefaction of lignocellulosic biomass for bio-oil, including upgrading methods, such as catalytic cracking and hydrogenation. Owing to the substantial amount of liquid fuels consumed by vehicular transport, converting biomass into drop-in liquid fuels may reduce the dependence of the fuel market on petroleum-based fuel products. In this review, we also summarize recent progress in technologies for large-scale equipment for direct thermochemical conversion. We focus on the technical aspects critical to commercialization of the technologies for production of liquid fuels from biomass, including feedstock type, cracking catalysts, catalytic cracking mechanisms, catalytic reactors, and biofuel properties. We also discuss future prospects for direct thermochemical conversion in biorefineries for the production of high grade biofuels.

Pt -based anode catalysts for direct ethanol fuel cells

International Nuclear Information System (INIS)

Hoyos, Bibian; Sanchez, Carlos; Gonzalez, Javier

2007-01-01

In this work it is studied the electro-catalytic behavior of pure platinum and platinum-based alloys with Ru, Sn, Ir, and Os supported on carbon to the ethanol electro-oxidation in aims to develop anodic catalysts for direct ethanol fuel cells, additionally, porous electrodes and membrane electrode assemblies were built for proton exchange membrane fuel cells in which the electrodes were tested. Catalysts characterization was made by cyclic voltammetry whereas the fuel cells behavior tests were made by current-potential polarization curves. in general, all alloys show a lower on-set reaction potential and a higher catalytic activity than pure platinum. However, in the high over potential zone, pure platinum has higher catalytic activity than the alloys. In agreement with these results, the alloys studied here could be useful in fuel cells operating on moderated and low current

Comprehensive Technical Report, General Electric Direct-Air-Cycle Aircraft Nuclear Propulsion Program, Program Summary and References

Energy Technology Data Exchange (ETDEWEB)

Thornton, G.; Rothstein, A.J.

1962-06-28

This is one of twenty-one volumes sumarizing the Aircraft Nuclear Propulsion Program of the General Electric Company. This volume discusses the background to the General Electric program, and summarizes the various direct-air-cycle nuclear test assemblies and power plants that were developed. Because of the requirements of high performance, low weight, and small size, vast improvements in existing technology were required to meet the flight objectives. The technological progress achieved during the program is also summarized. The last appendix contains a compilation of the abstracts, tables of contents, and reference lists of the other twenty volumes.

Including lateral interactions into microkinetic models of catalytic reactions

DEFF Research Database (Denmark)

Hellman, Anders; Honkala, Johanna Karoliina

2007-01-01

In many catalytic reactions lateral interactions between adsorbates are believed to have a strong influence on the reaction rates. We apply a microkinetic model to explore the effect of lateral interactions and how to efficiently take them into account in a simple catalytic reaction. Three differ...... different approximations are investigated: site, mean-field, and quasichemical approximations. The obtained results are compared to accurate Monte Carlo numbers. In the end, we apply the approximations to a real catalytic reaction, namely, ammonia synthesis....

Population exposure from the nuclear fuel cycle: Review and future direction

International Nuclear Information System (INIS)

Richmond, C.R.

1988-01-01

The legacy of radiation exposures confronting man arises from two historical sources of energy, the sun and radioactive decay. Contemporary man continues to be dependent on these two energy sources, which include the nuclear fuel cycle. Radiation exposures from all energy sources should be examined, with particular emphasis on the nuclear fuel cycle, including incidents such as Chernobyl and Three Mile Island. In addition to risk estimation, concepts such as de minimis, life shortening as a measure of risk, and competing risks as projected into the future must be considered in placing radiation exposures in perspective. The utility of these concepts is in characterizing population exposures for decision makers in a manner that the public may judge acceptable. All these viewpoints are essential in the evaluation of population exposure from the nuclear fuel cycle

Direct radioimmunoassay of urinary estrogen and pregnanediol glucuronides during the menstrual cycle

Energy Technology Data Exchange (ETDEWEB)

Stanczyk, F.Z.; Miyakawa, I.; Goebelsmann, U.

1980-06-15

Assays measuring immunoreactive estrone glucuronide (E/sub 1/G), estradiol-3-glucuronide (E/sub 2/-3G), estradiol-17..beta..-glucuronide (E/sub 2/-17G), estriol-3-glucuronide (E/sub 3/-3G), estriol-16..cap alpha..-glucuronide (E/sub 3/-16G), and pregnanediol-3..cap alpha..-glucuronide (Pd-3G) directly in diluted urine were developed and validated. These estrogen and pregnanediol glucuronide fractions were measured in aliquots of 24-hour and overnight samples of urine collected daily from seven women for one menstrual cycle. Urinary hormone excretion was correlated with daily serum estradiol (E/sub 2/), progesterone (P), and lutenizing hormonee (LH) levels. A sharp midcycle LH peak preceded by a preovulatory rise in serum E/sub 2/ and followed by luteal phase serum P levels were noted in each of the seven apparently ovulatory cycles. Twenty-four-hour and overnight urinary excretion patterns of estrogen glucuronides were similar to those of serum E/sub 2/. Of the five estrogen glucuronide fractions tested, excretion of E/sub 2/-17G exhibited the earliest and steepest ascending slope of the preovulatory estrogen surge and correlated best with serum E/sub 2/ levels. Urinary excretion of E/sub 1/-G, E/sub 2/-3G, and E/sub 3/-16G also showed an early and steep preovulatory rise and preceded that of E/sub 3/-3G, whereas urinary excretion of E/sub 3/-3G exhibited the poorest correlation with serum E/sub 2/ concentrations. The urinary excretion of Pd-3G rose parallel to serum P levels and was markedly elevated 2 to 3 days after the midcycle LH peak in both 24-hour and overnight collections of urine. These results indicate that among the urinary estrogen conjugate fractions tested, E/sub 2/-17G is the one that most suitably predicts ovulation.

Direct radioimmunoassay of urinary estrogen and pregnanediol glucuronides during the menstrual cycle

International Nuclear Information System (INIS)

Stanczyk, F.Z.; Miyakawa, I.; Goebelsmann, U.

1980-01-01

Assays measuring immunoreactive estrone glucuronide (E 1 G), estradiol-3-glucuronide (E 2 -3G), estradiol-17β-glucuronide (E 2 -17G), estriol-3-glucuronide (E 3 -3G), estriol-16α-glucuronide (E 3 -16G), and pregnanediol-3α-glucuronide (Pd-3G) directly in diluted urine were developed and validated. These estrogen and pregnanediol glucuronide fractions were measured in aliquots of 24-hour and overnight samples of urine collected daily from seven women for one menstrual cycle. Urinary hormone excretion was correlated with daily serum estradiol (E 2 ), progesterone (P), and lutenizing hormonee (LH) levels. A sharp midcycle LH peak preceded by a preovulatory rise in serum E 2 and followed by luteal phase serum P levels were noted in each of the seven apparently ovulatory cycles. Twenty-four-hour and overnight urinary excretion patterns of estrogen glucuronides were similar to those of serum E 2 . Of the five estrogen glucuronide fractions tested, excretion of E 2 -17G exhibited the earliest and steepest ascending slope of the preovulatory estrogen surge and correlated best with serum E 2 levels. Urinary excretion of E 1 -G, E 2 -3G, and E 3 -16G also showed an early and steep preovulatory rise and preceded that of E 3 -3G, whereas urinary excretion of E 3 -3G exhibited the poorest correlation with serum E 2 concentrations. The urinary excretion of Pd-3G rose parallel to serum P levels and was markedly elevated 2 to 3 days after the midcycle LH peak in both 24-hour and overnight collections of urine. These results indicate that among the urinary estrogen conjugate fractions tested, E 2 -17G is the one that most suitably predicts ovulation

Catalytic conversion of ethanol on H-Y zeolite

Directory of Open Access Journals (Sweden)

Čegar Nedeljko

2005-01-01

Full Text Available The catalytic activity of the H-form of synthetic zeolite NaY was examined in this study. The catalytic activity was determined according to the rate of ethanol conversion in a gas phase in the static system. In the conversion of ethanol on synthetic NaY zeolite at 585, 595, and 610 K, on which the reaction develops at an optimal rate, ethene and diethyl ether are evolved in approximately the same quantity. After transforming the NaY zeolite into the H-form, its catalytic activity was extremely increases so, the reaction develops at a significantly lower temperature with a very large increase in the reaction rate. The distribution of the products also changes, so that at lower temperatures diethyl ether is elvolved in most cases, and the development of ethene is favored at higher ones, and after a certain period of time there is almost complete conversion of ethanol into ethene. The increase in catalytic activity, as well as the change of selectivity of conversion of ethanol on the H-form of zeolite, is the result of removing Na+ cations in the NaY zeolite, so that more acidic catalyst is obtained which contains a number of acidic catalytically active centers, as well as a more powerful one compared to the original NaY zeolite.

Catalytic characterization of bi-functional catalysts derived from Pd ...

Indian Academy of Sciences (India)

Unknown

1995; Lyubovsky and Pfefferle 1999; Sales et al 1999;. Hill et al 2000). ... For a catalytic system, whose activity ... catalytic systems containing Pd, supported on various acid- ..... Further studies are needed to optimize a balance between.

Catalytic membrane in reduction of aqueous nitrates: operational principles and catalytic performance

NARCIS (Netherlands)

Ilinitch, O.M.; Cuperus, F.P.; Nosova, L.V.; Gribov, E.N.

2000-01-01

The catalytic membrane with palladium-copper active component supported over the macroporous ceramic membrane, and a series of γ-Al 2O 3 supported Pd-Cu catalysts were prepared and investigated. In reduction of nitrate ions by hydrogen in water at ambient temperature, pronounced internal diffusion

Performance analysis of an Integrated Solar Combined Cycle using Direct Steam Generation in parabolic trough collectors

International Nuclear Information System (INIS)

Montes, M.J.; Rovira, A.; Munoz, M.; Martinez-Val, J.M.

2011-01-01

Highlights: → Solar hybridization improves the performance of CCGT in a very hot and dry weather. → The scheme analyzed is a DSG parabolic trough field coupled to the Rankine cycle. → An annual simulation has been carried out for two locations: Almeria and Las Vegas. → Economical analysis shows that this scheme is a cheaper way to exploit solar energy. → For that, solar hybridization must be limited to a small fraction of the CCGT power. - Abstract: The contribution of solar thermal power to improve the performance of gas-fired combined cycles in very hot and dry environmental conditions is analyzed in this work, in order to assess the potential of this technique, and to feature Direct Steam Generation (DSG) as a well suited candidate for achieving very good results in this quest. The particular Integrated Solar Combined Cycle (ISCC) power plant proposed consists of a DSG parabolic trough field coupled to the bottoming steam cycle of a Combined Cycle Gas Turbine (CCGT) power plant. For this analysis, the solar thermal power plant performs in a solar dispatching mode: the gas turbine always operates at full load, only depending on ambient conditions, whereas the steam turbine is somewhat boosted to accommodate the thermal hybridization from the solar field. Although the analysis is aimed to studying such complementary effects in the widest perspective, two relevant examples are given, corresponding to two well-known sites: Almeria (Spain), with a mediterranean climate, and Las Vegas (USA), with a hot and dry climate. The annual simulations show that, although the conventional CCGT power plant works worse in Las Vegas, owing to the higher temperatures, the ISCC system operates better in Las Vegas than in Almeria, because of solar hybridization is especially well coupled to the CCGT power plant in the frequent days with great solar radiation and high temperatures in Las Vegas. The complementary effect will be clearly seen in these cases, because the thermal

Hydrogen Production From catalytic reforming of greenhouse gases ...

African Journals Online (AJOL)

ADOWIE PERE

a fixed bed stainless steel reactor. The 20wt%. ... catalytic activity for hydrogen production with the highest yield and selectivity of 32.5% and 17.6% respectively. © JASEM ... CO2 reforming of methane is however not fully developed ..... Design and preparation of .... catalytic nickel membrane for gas to liquid (GTL) process.

Catalytic and recyclability properties of phytogenic copper oxide nanoparticles derived from Aglaia elaeagnoidea flower extract

Directory of Open Access Journals (Sweden)

G. Manjari

2017-07-01

Full Text Available The phytogenic synthesis method to highly active, recoverable and recyclable heterogeneous copper oxide nanocatalyst and encapsulated within biomaterial that acts as a nontoxic and renewable source of reducing and stabilizing agent. The biosynthesized CuO NPs were characterized using UV–Vis absorption spectroscopy, X-ray diffraction (XRD, field emission scanning electron microscopy (FESEM, energy dispersive X-ray spectroscopy (EDX, transmission electron microscopy (TEM and thermo gravimetric analysis-differential scanning calorimetry (TGA–DSC, techniques. The formation of CuO NPs with the size 20–45 nm range is shown in TEM image. Significantly, in aqueous phase CuO NPs have high catalytic activity for the reduction of Congo red (CR, methylene blue (MB and 4-nitrophenol (4-NP in the presence of the sodium borohydride (NaBH4 at room temperature. In addition, CuO NPs catalyst can be easily recovered by centrifugation and reused for 6 cycles with more than 90% conversion efficiency. CuO nanocatalyst, leaching after catalytic application was investigated by ICPAES (Inductively coupled plasma atomic emission spectroscopy. CuO NPs possess great prospects in reduction of pernicious dyes and nitro organic pollutants in water.

The effect of oxygen storage capacity on the dynamic characteristics of an automotive catalytic converter

Energy Technology Data Exchange (ETDEWEB)

Shamim, Tariq [Department of Mechanical Engineering, The University of Michigan-Dearborn, Dearborn, MI 48128-2406 (United States)

2008-11-15

Automotive catalytic converters, which are employed to reduce engine exhaust emissions, are subjected to highly transient conditions during a typical driving cycle. These transient conditions arise from changes in driving mode, the hysteresis and flow lags of the feedback control system, and result in fluctuations of air-fuel ratio, exhaust gas flow rates and temperatures. The catalyst performance is also strongly influenced by the oxygen storage capacity. This paper presents a computational investigation of the effect of oxygen storage capacity on the dynamic behavior of an automotive catalytic converter subjected to modulations in exhaust gases. The modulations are generated by forcing the temporal variations in exhaust gases air-fuel ratio, gas flow rates and temperatures. The study employs a single-channel based, one-dimensional, non-adiabatic model. The results show that the imposed modulations cause a significant departure in the catalyst behavior from its steady behavior, and the oxygen storage capacity plays an important role in determining the catalyst's response to the imposed modulations. Modulations and oxygen storage capacity are found to have relatively greater influence on the catalyst's performance near stoichiometric conditions. (author)

Cycle inhibiting factors (CIFs are a growing family of functional cyclomodulins present in invertebrate and mammal bacterial pathogens.

Directory of Open Access Journals (Sweden)

Grégory Jubelin

Full Text Available The cycle inhibiting factor (Cif produced by enteropathogenic and enterohemorrhagic Escherichia coli was the first cyclomodulin to be identified that is injected into host cells via the type III secretion machinery. Cif provokes cytopathic effects characterized by G(1 and G(2 cell cycle arrests, accumulation of the cyclin-dependent kinase inhibitors (CKIs p21(waf1/cip1 and p27(kip1 and formation of actin stress fibres. The X-ray crystal structure of Cif revealed it to be a divergent member of a superfamily of enzymes including cysteine proteases and acetyltransferases that share a conserved catalytic triad. Here we report the discovery and characterization of four Cif homologs encoded by different pathogenic or symbiotic bacteria isolated from vertebrates or invertebrates. Cif homologs from the enterobacteria Yersinia pseudotuberculosis, Photorhabdus luminescens, Photorhabdus asymbiotica and the beta-proteobacterium Burkholderia pseudomallei all induce cytopathic effects identical to those observed with Cif from pathogenic E. coli. Although these Cif homologs are remarkably divergent in primary sequence, the catalytic triad is strictly conserved and was shown to be crucial for cell cycle arrest, cytoskeleton reorganization and CKIs accumulation. These results reveal that Cif proteins form a growing family of cyclomodulins in bacteria that interact with very distinct hosts including insects, nematodes and humans.

A new 3DOM Ce-Fe-Ti material for simultaneously catalytic removal of PM and NOx from diesel engines.

Science.gov (United States)

Cheng, Ying; Liu, Jian; Zhao, Zhen; Song, Weiyu; Wei, Yuechang

2018-01-15

A new 3DOM material was designed and synthesized for the simultaneous removal of PM (soot particulates) and NOx from diesel engine exhausts. The catalytic purification taking place over the material with double efficacy is cost-efficient. The contact between solid PM and catalyst active site has been process intensified by 3DOM unique structure. 3DOM Ce 0.7 Fe 0.2 Ti 0.1 O 2 catalyst possess a high SCR activity and an excellent selectivity to N 2 , giving a maximum concentration of CO 2 at 385°C for PM combustion and 100% NO conversion in the temperature range of 281-425°C. The dual redox cycles (Fe 3+ +Ce 3+ ↔Fe 2+ +Ce 4+ ,Fe 3+ +Ti 3+ ↔Fe 2+ +Ti 4+ ) and the excellent reducibility and sufficient acid sites of catalysts play key roles for the highly catalytic performance. Copyright © 2017 Elsevier B.V. All rights reserved.

Pretreated Landfill Gas Conversion Process via a Catalytic Membrane Reactor for Renewable Combined Fuel Cell-Power Generation

Directory of Open Access Journals (Sweden)

Zoe Ziaka

2013-01-01

Full Text Available A new landfill gas-based reforming catalytic processing system for the conversion of gaseous hydrocarbons, such as incoming methane to hydrogen and carbon oxide mixtures, is described and analyzed. The exit synthesis gas (syn-gas is fed to power effectively high-temperature fuel cells such as SOFC types for combined efficient electricity generation. The current research work is also referred on the description and design aspects of permreactors (permeable reformers carrying the same type of landfill gas-reforming reactions. Membrane reactors is a new technology that can be applied efficiently in such systems. Membrane reactors seem to perform better than the nonmembrane traditional reactors. The aim of this research includes turnkey system and process development for the landfill-based power generation and fuel cell industries. Also, a discussion of the efficient utilization of landfill and waste type resources for combined green-type/renewable power generation with increased processing capacity and efficiency via fuel cell systems is taking place. Moreover, pollution reduction is an additional design consideration in the current catalytic processors fuel cell cycles.

Enhanced propylene production in FCC by novel catalytic materials

Energy Technology Data Exchange (ETDEWEB)

Kelkar, C.P.; Harris, D.; Xu, M.; Fu, J. [BASF Catalyst LLC, Iselin, NJ (United States)

2007-07-01

Fluid catalytic cracking is expected to increasingly supply the additional incremental requirements for propylene. The most efficient route to increase propylene yield from an FCC unit is through the use of medium pore zeolites such as ZSM-5. ZSM-5 zeolite cracks near linear olefins in the gasoline range to LPG olefins such as propylene and butylenes. This paper will describe catalytic approaches to increase gasoline range olefins and the chemistry of ZSM-5 to crack those olefins. The paper will also describe novel catalytic materials designed to increase propylene. (orig.)

Numerical simulation of a Linear Fresnel Reflector Concentrator used as direct generator in a Solar-GAX cycle

Energy Technology Data Exchange (ETDEWEB)

Velazquez, N.; Sauceda, D.; Beltran, R. [Instituto de Ingenieria, Universidad Autonoma de Baja California, Blvd. Benito Juarez y Calle de la Normal s/n, Mexicali, Baja California 21280 (Mexico); Garcia-Valladares, O. [Centro de Investigacion en Energia, Universidad Nacional Autonoma de Mexico, Privada Xochicalco s/n, Temixco, Morelos 62580 (Mexico)

2010-03-15

In this work a methodological analysis to design and evaluate the technical feasibility of use a Linear Fresnel Reflector Concentrator (LFRC) as generator in an advanced absorption refrigeration system (Solar-GAX cycle) has been carried out. For this purpose, a detailed one-dimensional numerical simulation of the thermal and fluid-dynamic behavior of a LFRC that solves, in a segregated manner, four subroutines: (a) fluid flow inside the receptor tube, (b) heat transfer in the receptor tube wall, (c) heat transfer in cover tube wall, and (d) solar thermal analysis in the solar concentrator has been developed. The LFRC numerical model has been validated with experimental data obtained from the technical literature; after that, a parametric study for different configurations of design has been carried out in order to obtain the highest solar concentration with the lowest thermal losses, keeping in mind both specific weather conditions and construction restrictions. The numerical result obtained demonstrates that using a LFRC as a direct generator in a Solar-GAX cycle satisfy not only the quantity and quality of the energy demanded by the advanced cooling system, it also allows to obtain higher global efficiencies of the system due to it can be operated in conditions where the maximum performance of the Solar-GAX cycle is obtained without affecting in any significant way the solar collector efficiency. (author)

Numerical simulation of a Linear Fresnel Reflector Concentrator used as direct generator in a Solar-GAX cycle

International Nuclear Information System (INIS)

Velazquez, N.; Garcia-Valladares, O.; Sauceda, D.; Beltran, R.

2010-01-01

In this work a methodological analysis to design and evaluate the technical feasibility of use a Linear Fresnel Reflector Concentrator (LFRC) as generator in an advanced absorption refrigeration system (Solar-GAX cycle) has been carried out. For this purpose, a detailed one-dimensional numerical simulation of the thermal and fluid-dynamic behavior of a LFRC that solves, in a segregated manner, four subroutines: (a) fluid flow inside the receptor tube, (b) heat transfer in the receptor tube wall, (c) heat transfer in cover tube wall, and (d) solar thermal analysis in the solar concentrator has been developed. The LFRC numerical model has been validated with experimental data obtained from the technical literature; after that, a parametric study for different configurations of design has been carried out in order to obtain the highest solar concentration with the lowest thermal losses, keeping in mind both specific weather conditions and construction restrictions. The numerical result obtained demonstrates that using a LFRC as a direct generator in a Solar-GAX cycle satisfy not only the quantity and quality of the energy demanded by the advanced cooling system, it also allows to obtain higher global efficiencies of the system due to it can be operated in conditions where the maximum performance of the Solar-GAX cycle is obtained without affecting in any significant way the solar collector efficiency.

A study on naphtha catalytic reforming reactor simulation and analysis.

Science.gov (United States)

Liang, Ke-min; Guo, Hai-yan; Pan, Shi-wei

2005-06-01

A naphtha catalytic reforming unit with four reactors in series is analyzed. A physical model is proposed to describe the catalytic reforming radial flow reactor. Kinetics and thermodynamics equations are selected to describe the naphtha catalytic reforming reactions characteristics based on idealizing the complex naphtha mixture by representing the paraffin, naphthene, and aromatic groups by single compounds. The simulation results based above models agree very well with actual operation unit data.

A study on naphtha catalytic reforming reactor simulation and analysis

OpenAIRE

Liang, Ke-min; Guo, Hai-yan; Pan, Shi-wei

2005-01-01

A naphtha catalytic reforming unit with four reactors in series is analyzed. A physical model is proposed to describe the catalytic reforming radial flow reactor. Kinetics and thermodynamics equations are selected to describe the naphtha catalytic reforming reactions characteristics based on idealizing the complex naphtha mixture by representing the paraffin, naphthene, and aromatic groups by single compounds. The simulation results based above models agree very well with actual operation uni...

Catalytic hydrogen recombination for nuclear containments

International Nuclear Information System (INIS)

Koroll, G.W.; Lau, D.W.P.; Dewit, W.A.; Graham, W.R.C.

1994-01-01

Catalytic recombiners appear to be a credible option for hydrogen mitigation in nuclear containments. The passive operation, versatility and ease of back fitting are appealing for existing stations and new designs. Recently, a generation of wet-proofed catalyst materials have been developed at AECL which are highly specific to H 2 -O 2 , are active at ambient temperatures and are being evaluated for containment applications. Two types of catalytic recombiners were evaluated for hydrogen removal in containments based on the AECL catalyst. The first is a catalytic combustor for application in existing air streams such as provided by fans or ventilation systems. The second is an autocatalytic recombiner which uses the enthalpy of reaction to produce natural convective flow over the catalyst elements. Intermediate-scale results obtained in 6 m 3 and 10 m 3 spherical and cylindrical vessels are given to demonstrate self-starting limits, operating limits, removal capacity, scaling parameters, flow resistance, mixing behaviour in the vicinity of an operating recombiner and sensitivity to poisoning, fouling and radiation. (author). 13 refs., 10 figs

Electrochemical catalytic treatment of phenol wastewater

International Nuclear Information System (INIS)

Ma Hongzhu; Zhang Xinhai; Ma Qingliang; Wang Bo

2009-01-01

The slurry bed catalytic treatment of contaminated water appears to be a promising alternative for the oxidation of aqueous organic pollutants. In this paper, the electrochemical oxidation of phenol in synthetic wastewater catalyzed by ferric sulfate and potassium permanganate adsorbed onto active bentonite in slurry bed electrolytic reactor with graphite electrode has been investigated. In order to determine the optimum operating condition, the orthogonal experiments were devised and the results revealed that the system of ferric sulfate, potassium permanganate and active bentonite showed a high catalytic efficiency on the process of electrochemical oxidation phenol in initial pH 5. When the initial concentration of phenol was 0.52 g/L (the initial COD 1214 mg/L), up to 99% chemical oxygen demand (COD) removal was obtained in 40 min. According to the experimental results, a possible mechanism of catalytic degradation of phenol was proposed. Environmental estimation was also done and the results showed that the treated wastewater have little impact on plant growth and could totally be applied to irrigation.

Electrochemical catalytic treatment of phenol wastewater

Energy Technology Data Exchange (ETDEWEB)

Ma Hongzhu, E-mail: hzmachem@snnu.edu.cn [Institute of Energy Chemistry, School of Chemistry and Materials Science, Shaanxi Normal University, Xi' an 710062 (China); Zhang Xinhai [Institute of Energy Chemistry, School of Chemistry and Materials Science, Shaanxi Normal University, Xi' an 710062 (China); Ma Qingliang [Department of Applied Physics, College of Sciences, Taiyuan University of Technology, 030024 Taiyuan (China); Wang Bo [Institute of Energy Chemistry, School of Chemistry and Materials Science, Shaanxi Normal University, Xi' an 710062 (China)

2009-06-15

The slurry bed catalytic treatment of contaminated water appears to be a promising alternative for the oxidation of aqueous organic pollutants. In this paper, the electrochemical oxidation of phenol in synthetic wastewater catalyzed by ferric sulfate and potassium permanganate adsorbed onto active bentonite in slurry bed electrolytic reactor with graphite electrode has been investigated. In order to determine the optimum operating condition, the orthogonal experiments were devised and the results revealed that the system of ferric sulfate, potassium permanganate and active bentonite showed a high catalytic efficiency on the process of electrochemical oxidation phenol in initial pH 5. When the initial concentration of phenol was 0.52 g/L (the initial COD 1214 mg/L), up to 99% chemical oxygen demand (COD) removal was obtained in 40 min. According to the experimental results, a possible mechanism of catalytic degradation of phenol was proposed. Environmental estimation was also done and the results showed that the treated wastewater have little impact on plant growth and could totally be applied to irrigation.

Effects of Direct Fuel Injection Strategies on Cycle-by-Cycle Variability in a Gasoline Homogeneous Charge Compression Ignition Engine: Sample Entropy Analysis

Directory of Open Access Journals (Sweden)

Jacek Hunicz

2015-01-01

Full Text Available In this study we summarize and analyze experimental observations of cyclic variability in homogeneous charge compression ignition (HCCI combustion in a single-cylinder gasoline engine. The engine was configured with negative valve overlap (NVO to trap residual gases from prior cycles and thus enable auto-ignition in successive cycles. Correlations were developed between different fuel injection strategies and cycle average combustion and work output profiles. Hypothesized physical mechanisms based on these correlations were then compared with trends in cycle-by-cycle predictability as revealed by sample entropy. The results of these comparisons help to clarify how fuel injection strategy can interact with prior cycle effects to affect combustion stability and so contribute to design control methods for HCCI engines.

Cellulosic Biomass Sugars to Advantaged Jet Fuel – Catalytic Conversion of Corn Stover to Energy Dense, Low Freeze Point Paraffins and Naphthenes

Energy Technology Data Exchange (ETDEWEB)

Cortright, Randy [Virent, Inc., Madison, WI (United States)

2015-07-31

The purpose of this project was to demonstrate the technical and commercial feasibility of producing liquid fuels, particularly jet fuel, from lignocellulosic materials, such as corn stover. This project was led by Virent, Inc. (Virent) which has developed a novel chemical catalytic process (the BioForming^® platform) capable of producing “direct replacement” liquid fuels from biomass-derived feedstocks. Virent has shown it is possible to produce an advantaged jet fuel from biomass that meets or exceeds specifications for commercial and military jet fuel through Fuel Readiness Level (FRL) 5, Process Validation. This project leveraged The National Renewable Energy Lab’s (NREL) expertise in converting corn stover to sugars via dilute acid pretreatment and enzymatic hydrolysis. NREL had previously developed this deconstruction technology for the conversion of corn stover to ethanol. In this project, Virent and NREL worked together to condition the NREL generated hydrolysate for use in Virent’s catalytic process through solids removal, contaminant reduction, and concentration steps. The Idaho National Laboratory (INL) was contracted in this project for the procurement, formatting, storage and analysis of corn stover and Northwestern University developed fundamental knowledge of lignin deconstruction that can help improve overall carbon recovery of the combined technologies. Virent conducted fundamental catalytic studies to improve the performance of the catalytic process and NREL provided catalyst characterization support. A technoeconomic analysis (TEA) was conducted at each stage of the project, with results from these analyses used to inform the direction of the project.

Direct electrochemistry of nitrate reductase from the fungus Neurospora crassa.

Science.gov (United States)

Kalimuthu, Palraj; Ringel, Phillip; Kruse, Tobias; Bernhardt, Paul V

2016-09-01

We report the first direct (unmediated) catalytic electrochemistry of a eukaryotic nitrate reductase (NR). NR from the filamentous fungus Neurospora crassa, is a member of the mononuclear molybdenum enzyme family and contains a Mo, heme and FAD cofactor which are involved in electron transfer from NAD(P)H to the (Mo) active site where reduction of nitrate to nitrite takes place. NR was adsorbed on an edge plane pyrolytic graphite (EPG) working electrode. Non-turnover redox responses were observed in the absence of nitrate from holo NR and three variants lacking the FAD, heme or Mo cofactor. The FAD response is due to dissociated cofactor in all cases. In the presence of nitrate, NR shows a pronounced cathodic catalytic wave with an apparent Michaelis constant (KM) of 39μM (pH7). The catalytic cathodic current increases with temperature from 5 to 35°C and an activation enthalpy of 26kJmol(-1) was determined. In spite of dissociation of the FAD cofactor, catalytically activity is maintained. Copyright © 2016. Published by Elsevier B.V.

Sintering of Catalytic Nanoparticles: Particle Migration or Ostwald Ripening?

DEFF Research Database (Denmark)

Hansen, Thomas Willum; DeLaRiva, Andrew T.; Challa, Sivakumar R.

2013-01-01

deactivation, is an important mechanism for the loss of catalyst activity. This is especially true for high temperature catalytic processes, such as steam reforming, automotive exhaust treatment, or catalytic combustion. With dwindling supplies of precious metals and increasing demand, fundamental...

Catalytic synthesis of ammonia using vibrationally excited nitrogen molecules

DEFF Research Database (Denmark)

Hansen, Flemming Yssing; Henriksen, Niels Engholm; Billing, Gert D.

1992-01-01

The dissociation of nitrogen is the rate-limiting step in the catalytic synthesis of ammonia. Theoretical calculations have shown that the dissociative sticking probability of molecular nitrogen on catalytic active metal surfaces is enhanced by orders of magnitude when the molecules...

Direct ethanol solid oxide fuel cell operating in gradual internal reforming

Science.gov (United States)

Nobrega, S. D.; Galesco, M. V.; Girona, K.; de Florio, D. Z.; Steil, M. C.; Georges, S.; Fonseca, F. C.

2012-09-01

An electrolyte supported solid oxide fuel cell (SOFC) using standard electrodes, doped-lanthanum manganite cathode and Ni-cermet anode, was operated with direct (anhydrous) ethanol for more than 100 h, delivering essentially the same power output as running on hydrogen. A ceria-based layer provides the catalytic activity for the gradual internal reforming, which uses the steam formed by the electrochemical oxidation of hydrogen for the decomposition of ethanol. Such a concept opens up the way for multi-fuel SOFCs using standard components and a catalytic layer.

Determination of Model Kinetics for Forced Unsteady State Operation of Catalytic CH4 Oxidation

Directory of Open Access Journals (Sweden)

Effendy Mohammad

2016-01-01

Full Text Available The catalytic oxidation of methane for abating the emission vented from coal mine or natural gas transportation has been known as most reliable method. A reverse flow reactor operation has been widely used to oxidize this methane emission due to its capability for autothermal operation and heat production. The design of the reverse flow reactor requires a proper kinetic rate expression, which should be developed based on the operating condition. The kinetic rate obtained in the steady state condition cannot be applied for designing the reactor operated under unsteady state condition. Therefore, new approach to develop the dynamic kinetic rate expression becomes indispensable, particularly for periodic operation such as reverse flow reactor. This paper presents a novel method to develop the kinetic rate expression applied for unsteady state operation. The model reaction of the catalytic methane oxidation over Pt/-Al2O3 catalyst was used with kinetic parameter determined from laboratory experiments. The reactor used was a fixed bed, once-through operation, with a composition modulation in the feed gas. The switching time was set at 3 min by varying the feed concentration, feed flow rate, and reaction temperature. The concentrations of methane in the feed and product were measured and analysed using gas chromatography. The steady state condition for obtaining the kinetic rate expression was taken as a base case and as a way to judge its appropriateness to be applied for dynamic system. A Langmuir-Hinshelwood reaction rate model was developed. The time period during one cycle was divided into some segments, depending on the ratio of CH4/O2. The experimental result shows that there were kinetic regimes occur during one cycle: kinetic regime controlled by intrinsic surface reaction and kinetic regime controlled by external diffusion. The kinetic rate obtained in the steady state operation was not appropriate when applied for unsteady state operation

Upgrading of bio-oil to boiler fuel by catalytic hydrotreatment and esterification in an efficient process

International Nuclear Information System (INIS)

Zhang, Xinghua; Chen, Lungang; Kong, Wei; Wang, Tiejun; Zhang, Qi; Long, Jinxing; Xu, Ying; Ma, Longlong

2015-01-01

Bio-oil can't be directly used as fuel due to its deteriorate properties. Here, an efficient catalytic upgrading process for the bio-oil, including esterification, hydrogenation, hydrodeoxygenation and depolymerization, is proposed with multifunctional catalyst Ni/SiO 2 –ZrO 2 and biomass-derived solvent ethanol. Results showed that esters, alcohols, phenolics, and cyclo-ketones were the main components in the upgraded bio-oil while aldehydes were removed completely via catalytic hydrogenation and acids were removed by catalytic esterification with supercritical ethanol. The pH value of upgraded bio-oil rose drastically from 2.38 to 5.24, and the high heating value increased to 24.4 MJ kg −1 . Comparison characterization on the upgraded and crude bio-oil using FT-IR, GPC (Gel permeation chromatography) and 13 C NMR (Nuclear Magnetic Resonance) demonstrated that lignin-derived oligomers contained in crude bio-oil were further depolymerized over Ni/SiO 2 –ZrO 2 catalyst. The improved properties suggest that the upgraded bio-oil is more suitable to be used as boiler fuel. Furthermore, the loss of carbon is negligible because formation of coke is suppressed during the upgrading process. - Highlights: • Acid can be converted via catalytic esterification in supercritical ethanol. • Aldehydes can be removed completely during the upgrading process. • Lignin-derived oligomers were further depolymerized during the upgrading process. • Formation of coke is effectively inhibited during the upgrading process

Dissecting the Catalytic Mechanism of Betaine-Homocysteine S-Methyltransferase Using Intrinsic Tryptophan Fluorescence and Site-Directed Mutagenesis

Energy Technology Data Exchange (ETDEWEB)

Castro, C.; Gratson, A.A.; Evans, J.C.; Jiracek, J.; Collinsova, M.; Ludwig, M.L.; Garrow, T.A. (ASCR); (UIUC); (Michigan)

2010-03-05

Betaine-homocysteine S-methyltransferase (BHMT) is a zinc-dependent enzyme that catalyzes the transfer of a methyl group from glycine betaine (Bet) to homocysteine (Hcy) to form dimethylglycine (DMG) and methionine (Met). Previous studies in other laboratories have indicated that catalysis proceeds through the formation of a ternary complex, with a transition state mimicked by the inhibitor S-({delta}-carboxybutyl)-l-homocysteine (CBHcy). Using changes in intrinsic tryptophan fluorescence to determine the affinity of human BHMT for substrates, products, or CBHcy, we now demonstrate that the enzyme-substrate complex reaches its transition state through an ordered bi-bi mechanism in which Hcy is the first substrate to bind and Met is the last product released. Hcy, Met, and CBHcy bind to the enzyme to form binary complexes with K{sub d} values of 7.9, 6.9, and 0.28 {micro}M, respectively. Binary complexes with Bet and DMG cannot be detected with fluorescence as a probe, but Bet and DMG bind tightly to BHMT-Hcy to form ternary complexes with K{sub d} values of 1.1 and 0.73 {micro}M, respectively. Mutation of each of the seven tryptophan residues in human BHMT provides evidence that the enzyme undergoes two distinct conformational changes that are reflected in the fluorescence of the enzyme. The first is induced when Hcy binds, and the second, when Bet binds. As predicted by the crystal structure of BHMT, the amino acids Trp44 and Tyr160 are involved in binding Bet, and Glu159 in binding Hcy. Replacing these residues by site-directed mutagenesis significantly reduces the catalytic efficiency (V{sub max}/K{sub m}) of the enzyme. Replacing Tyr77 with Phe abolishes enzyme activity.

Credit cycles and macro fundamentals

NARCIS (Netherlands)

Koopman, S.J.; Kraeussl, R.G.W.; Lucas, A.; Monteiro, A.

2009-01-01

We use an intensity-based framework to study the relation between macroeconomic fundamentals and cycles in defaults and rating activity. Using Standard and Poor's U.S. corporate rating transition and default data over the period 1980-2005, we directly estimate the default and rating cycle from micro

Structured materials for catalytic and sensing applications

Science.gov (United States)

Hokenek, Selma

The optical and chemical properties of the materials used in catalytic and sensing applications directly determine the characteristics of the resultant catalyst or sensor. It is well known that a catalyst needs to have high activity, selectivity, and stability to be viable in an industrial setting. The hydrogenation activity of palladium catalysts is known to be excellent, but the industrial applications are limited by the cost of obtaining catalyst in amounts large enough to make their use economical. As a result, alloying palladium with a cheaper, more widely available metal while maintaining the high catalytic activity seen in monometallic catalysts is, therefore, an attractive option. Similarly, the optical properties of nanoscale materials used for sensing must be attuned to their application. By adjusting the shape and composition of nanoparticles used in such applications, very fine changes can be made to the frequency of light that they absorb most efficiently. The design, synthesis, and characterization of (i) size controlled monometallic palladium nanoparticles for catalytic applications, (ii) nickel-palladium bimetallic nanoparticles and (iii) silver-palladium nanoparticles with applications in drug detection and biosensing through surface plasmon resonance, respectively, will be discussed. The composition, size, and shape of the nanoparticles formed were controlled through the use of wet chemistry techniques. After synthesis, the nanoparticles were analyzed using physical and chemical characterization techniques such as X-Ray Diffraction (XRD), Transmission Electron Microscopy (TEM), and Scanning Transmission Electron Microscopy- Energy-Dispersive Spectrometry (STEM-EDX). The Pd and Ni-Pd nanoparticles were then supported on silica for catalytic testing using mass spectrometry. The optical properties of the Ag-Pd nanoparticles in suspension were further investigated using ultraviolet-visible spectrometry (UV-Vis). Monometallic palladium particles have

Reactivity of organic compounds in catalytic synthesis

Energy Technology Data Exchange (ETDEWEB)

Minachev, Kh M; Bragin, O V

1978-01-01

A comprehensive review of 1976 Soviet research on catalysis delivered to the 1977 annual session of the USSR Academy of Science Council on Catalysis (Baku 6/16-20/77) covers hydrocarbon reactions, including hydrogenation and hydrogenolysis, dehydrogenation, olefin dimerization and disproportionation, and cyclization and dehydrocyclization (e.g., piperylene cyclization and ethylene cyclotrimerization); catalytic and physicochemical properties of zeolites, including cracking, dehydrogenation, and hydroisomerization catalytic syntheses and conversion of heterocyclic and functional hydrocarbon derivatives, including partial and total oxidation (e.g., of o-xylene to phthalic anhydride); syntheses of thiophenes from alkanes and hydrogen sulfide over certain dehydrogenation catalysts; catalytic syntheses involving carbon oxides ( e.g., the development of a new heterogeneous catalyst for hydroformylation of olefins), and of Co-MgO zeolitic catalysts for synthesis of aliphatic hydrocarbons from carbon dioxide and hydrogen, and fabrication of high-viscosity lubricating oils over bifunctional aluminosilicate catalysts.

Driving and engine cycles

CERN Document Server

Giakoumis, Evangelos G

2017-01-01

This book presents in detail the most important driving and engine cycles used for the certification and testing of new vehicles and engines around the world. It covers chassis and engine-dynamometer cycles for passenger cars, light-duty vans, heavy-duty engines, non-road engines and motorcycles, offering detailed historical information and critical review. The book also provides detailed examples from SI and diesel engines and vehicles operating during various cycles, with a focus on how the engine behaves during transients and how this is reflected in emitted pollutants, CO2 and after-treatment systems operation. It describes the measurement methods for the testing of new vehicles and essential information on the procedure for creating a driving cycle. Lastly, it presents detailed technical specifications on the most important chassis-dynamometer cycles around the world, together with a direct comparison of those cycles.

Component Development to Accelerate Commercial Implementation of Ultra-Low Emissions Catalytic Combustion

Energy Technology Data Exchange (ETDEWEB)

McCarty, Jon; Berry, Brian; Lundberg, Kare; Anson, Orris

2003-03-31

This final report describes a 2000-2003 program for the development of components and processes to enhance the commercialization of ultra-low emissions catalytic combustion in industrial gas turbines. The range of project tasks includes: development of more durable, lower-cost catalysts and catalytic combustor components; development and design of a catalytic pre-burner and a catalytic pilot burner for gas turbines, and on-site fuel conversion processing for utilization of liquid fuel.

Direct chlorination of alcohols with chlorodimethylsilane catalyzed by a gallium trichloride/tartrate system under neutral conditions.

Science.gov (United States)

Yasuda, Makoto; Shimizu, Kenji; Yamasaki, Satoshi; Baba, Akio

2008-08-07

The reaction of secondary alcohols 1 with chlorodimethylsilane (HSiMe(2)Cl) proceeded in the presence of a catalytic amount of GaCl(3)/diethyl tartrate to give the corresponding organic chlorides 3. In the catalytic cycle, the reaction of diethyl tartrate 4a with HSiMe(2)Cl 2 gives the chlorosilyl ether 5 with generation of H(2). Alcohol-exchange between the formed chlorosilyl ether 5 and the substrate alcohol 1 affords alkoxychlorosilane 6, which reacts with catalytic GaCl(3) to give the chlorinated product 3. The moderate Lewis acidity of GaCl(3) facilitates chlorination. Strong Lewis acids did not give product due to excessive affinity for the oxy-functionalities. Although tertiary alcohols were chlorinated by this system even in the absence of diethyl tartrate, certain alcohols that are less likely to give carbocationic species were effectively chlorinated using the GaCl(3)/diethyl tartrate system.

Catalytic Conversion of Biofuels

DEFF Research Database (Denmark)

Jørgensen, Betina

This thesis describes the catalytic conversion of bioethanol into higher value chemicals. The motivation has been the unavoidable coming depletion of the fossil resources. The thesis is focused on two ways of utilising ethanol; the steam reforming of ethanol to form hydrogen and the partial oxida...

The template-assisted electrodeposition of platinum nanowires for catalytic applications

Directory of Open Access Journals (Sweden)

Soha Mohajeri

2018-05-01

Full Text Available Template-assisted electrodeposition technique was applied to synthesize platinum nanowires (Pt NWs on polycarbonate templates (PCT with pore diameters of 15, 50, and 100 nm for catalytic applications. Influences of sulfuric acid added to the electrolyte, different potential scanning rates and different pore diameters of templates on the electrodeposition process of Pt NWs were investigated by electrochemical techniques, including voltammetry and chronoamperometry methods. It was confirmed that at lower scan rates and in acidic solutions, electrodeposition of platinum on templates with larger pores is controlled by diffusion. The potential range for deposition of Pt NWs was determined and the potentiostatic technique was utilized by applying various potentials of different durations to fabricate the NWs. The morphological characteristics of Pt NWs were examined using the scanning electron microscopy (SEM. It was shown that the growth of Pt NWs on PCT 50 nm followed a pine-tree pattern, while the Pt NWs grew spherically on PCT 100 nm. The uniform and compact shape of Pt NWs was verified by the transmission electron microscopy (TEM. The catalytic activities of the prepared Pt NWs with the same exchanged charge density for hydrogen adsorption/desorption and methanol oxidation reactions were determined by the cyclic voltammetry (CV testing, and the superior electrocatalytic performance was detected for Pt NWs prepared on PCT 50 nm. This enhanced catalytic activity was attributed to the higher surface-to-volume ratio, larger electrochemical active surface area and higher density of exposed active sites accessible on the pine-tree morphology of these Pt NWs compared to the spherical structure of Pt NWs fabricated on PCT 100 nm. This makes Pt NWs prepared on PCT 50 nm to be a promising catalyst for direct methanol fuel cells (DMFCs.

Direct fabrication of metal-free hollow graphene balls with a self-supporting structure as efficient cathode catalysts of fuel cell

Energy Technology Data Exchange (ETDEWEB)

Lu, Yanqi; Liu, Mingda; Nie, Huagui, E-mail: huaguinie@126.com; Gu, Cancan; Liu, Ming; Yang, Zhi, E-mail: yang201079@126.com; Yang, Keqin; Chen, Xi’an; Huang, Shaoming, E-mail: smhuang@wzu.edu.cn [Wenzhou University, Nanomaterials and Chemistry Key Laboratory (China)

2016-06-15

Despite the good progress in developing carbon catalysts for oxygen reduction reaction (ORR), the current metal-free carbon catalysts are still far from satisfactory for large-scale applications of fuel cell. Developing hollow graphene balls with a self-supporting structure is considered to be an ideal method to inhibit graphene stacking and improve their catalytic performance. Herein, we fabricated metal-free hollow graphene balls with a self-supporting structure, through using a new strategy that involves direct metal-free catalytic growth from assembly of SiO{sub 2} spheres. To our knowledge, although much researches involving the synthesis of graphene balls have been reported, investigations into the direct metal-free catalytic growth of hollow graphene balls are rare. Furthermore, the electrocatalytic performance shows that the resulting hollow graphene balls have significantly high catalytic activity. More importantly, such catalysts also possess much improved stability and better methanol tolerance in alkaline media during the ORR compared with commercial Pt/C catalysts. The outstanding performances coupled with an easy and inexpensive preparing method indicated the great potential of the hollow graphene balls with a self-supporting structure in large-scale applications of fuel cell.Graphical AbstractHollow graphene balls with a self-supporting structure have been successfully fabricated, through using a new strategy that involves direct metal-free catalytic growth from 3D assembly of SiO{sub 2} spheres. The hollow graphene balls can exhibit a high catalytic activity, long-term stability, and an excellent methanol tolerance for the oxygen reduction reaction.

Direct fabrication of metal-free hollow graphene balls with a self-supporting structure as efficient cathode catalysts of fuel cell

International Nuclear Information System (INIS)

Lu, Yanqi; Liu, Mingda; Nie, Huagui; Gu, Cancan; Liu, Ming; Yang, Zhi; Yang, Keqin; Chen, Xi’an; Huang, Shaoming

2016-01-01

Despite the good progress in developing carbon catalysts for oxygen reduction reaction (ORR), the current metal-free carbon catalysts are still far from satisfactory for large-scale applications of fuel cell. Developing hollow graphene balls with a self-supporting structure is considered to be an ideal method to inhibit graphene stacking and improve their catalytic performance. Herein, we fabricated metal-free hollow graphene balls with a self-supporting structure, through using a new strategy that involves direct metal-free catalytic growth from assembly of SiO_2 spheres. To our knowledge, although much researches involving the synthesis of graphene balls have been reported, investigations into the direct metal-free catalytic growth of hollow graphene balls are rare. Furthermore, the electrocatalytic performance shows that the resulting hollow graphene balls have significantly high catalytic activity. More importantly, such catalysts also possess much improved stability and better methanol tolerance in alkaline media during the ORR compared with commercial Pt/C catalysts. The outstanding performances coupled with an easy and inexpensive preparing method indicated the great potential of the hollow graphene balls with a self-supporting structure in large-scale applications of fuel cell.Graphical AbstractHollow graphene balls with a self-supporting structure have been successfully fabricated, through using a new strategy that involves direct metal-free catalytic growth from 3D assembly of SiO_2 spheres. The hollow graphene balls can exhibit a high catalytic activity, long-term stability, and an excellent methanol tolerance for the oxygen reduction reaction

Direct view on the phase evolution in individual LiFePO4 nanoparticles during Li-ion battery cycling.

Science.gov (United States)

Zhang, Xiaoyu; van Hulzen, Martijn; Singh, Deepak P; Brownrigg, Alex; Wright, Jonathan P; van Dijk, Niels H; Wagemaker, Marnix

2015-09-23

Phase transitions in Li-ion electrode materials during (dis)charge are decisive for battery performance, limiting high-rate capabilities and playing a crucial role in the cycle life of Li-ion batteries. However, the difficulty to probe the phase nucleation and growth in individual grains is hindering fundamental understanding and progress. Here we use synchrotron microbeam diffraction to disclose the cycling rate-dependent phase transition mechanism within individual particles of LiFePO4, a key Li-ion electrode material. At low (dis)charge rates well-defined nanometer thin plate-shaped domains co-exist and transform much slower and concurrent as compared with the commonly assumed mosaic transformation mechanism. As the (dis)charge rate increases phase boundaries become diffuse speeding up the transformation rates of individual grains. Direct observation of the transformation of individual grains reveals that local current densities significantly differ from what has previously been assumed, giving new insights in the working of Li-ion battery electrodes and their potential improvements.

In situ catalytic growth of large-area multilayered graphene/MoS2 heterostructures

OpenAIRE

Fu, Wei; Du, Fei-Hu; Su, Juan; Li, Xin-Hao; Wei, Xiao; Ye, Tian-Nan; Wang, Kai-Xue; Chen, Jie-Sheng

2014-01-01

Stacking various two-dimensional atomic crystals on top of each other is a feasible approach to create unique multilayered heterostructures with desired properties. Herein for the first time, we present a controlled preparation of large-area graphene/MoS2 heterostructures via a simple heating procedure on Mo-oleate complex coated sodium sulfate under N2 atmosphere. Through a direct in situ catalytic reaction, graphene layer has been uniformly grown on the MoS2 film formed by the reaction of M...

Pd and polyaniline nanocomposite on carbon fiber paper as an efficient direct formic acid fuel cell anode

Science.gov (United States)

Pandey, Rakesh K.

2018-03-01

Direct formic acid fuel cells are advantageous as portable power generating devices. In the present work, an anode catalyst for direct formic acid fuel cell (DFAFC) is presented which has good catalytic activity for formic acid oxidation. The catalyst is composed of Pd and conducting polymer polyaniline (Pd-PANI) nanocomposite. The catalyst was prepared by using a single step galvanostatic electrochemical deposition method. The Pd-PANI catalyst was electrodeposited at different time durations and a comparison of the catalytic activity at each deposition time was carried out and optimized.

Highly efficient catalytic systems based on Pd-coated microbeads

Science.gov (United States)

Lim, Jin Hyun; Cho, Ahyoung; Lee, Seung Hwan; Park, Bumkyo; Kang, Dong Woo; Koo, Chong Min; Yu, Taekyung; Park, Bum Jun

2018-01-01

The efficiency of two prototype catalysis systems using palladium (Pd)-coated microparticles was investigated with regard to the recovery and recyclability of the catalytic particles. One such system was the interface-adsorption method, in which polymer particles coated with Pd nanoparticles strongly and irreversibly attach to the oil-water interface. Due to the irreversible adsorption of the catalytic particles to the interface, particle loss was completely prevented while mixing the aqueous solution and while collecting the products. The other system was based on the magnetic field-associated particle recovery method. The use of polymeric microparticles containing Pd nanoparticles and magnetite nanoparticles accelerated the sedimentation of the particles in the aqueous phase by applying a strong magnetic field, consequently suppressing drainage of the particles from the reactor along the product stream. Upon multiple runs of the catalytic reactions, it was found that conversion does not change significantly, demonstrating the excellent recyclability and performance efficiency in the catalytic processes.

Catalytic pyrolysis of microalgae to high-quality liquid bio-fuels

International Nuclear Information System (INIS)

Babich, I.V.; Hulst, M. van der; Lefferts, L.; Moulijn, J.A.; O'Connor, P.; Seshan, K.

2011-01-01

The pyrolytic conversion of chlorella algae to liquid fuel precursor in presence of a catalyst (Na 2 CO 3 ) has been studied. Thermal decomposition studies of the algae samples were performed using TGA coupled with MS. Liquid oil samples were collected from pyrolysis experiments in a fixed-bed reactor and characterized for water content and heating value. The oil composition was analyzed by GC-MS. Pretreatment of chlorella with Na 2 CO 3 influences the primary conversion of chlorella by shifting the decomposition temperature to a lower value. In the presence of Na 2 CO 3 , gas yield increased and liquid yield decreased when compared with non-catalytic pyrolysis at the same temperatures. However, pyrolysis oil from catalytic runs carries higher heating value and lower acidity. Lower content of acids in the bio-oil, higher aromatics, combined with higher heating value show promise for production of high-quality bio-oil from algae via catalytic pyrolysis, resulting in energy recovery in bio-oil of 40%. -- Highlights: → The pyrolytic catalytic conversion of chlorella algae to liquid fuel precursor. → Na 2 CO 3 as a catalyst for the primary conversion of chlorella. → Pyrolysis oil from catalytic runs carries higher heating value and lower acidity. → High-quality bio-oil from algae via catalytic pyrolysis with energy recovery in bio-oil of 40%.

Properties and application of noble metal catalysts for heterogeneous catalytic hydrogenations

Energy Technology Data Exchange (ETDEWEB)

Horn, G; Frohning, C D; Cornils, B [Ruhrchemie A.G., Oberhausen (Germany, F.R.)

1976-07-01

The special properties of the six platinum group elements - ruthenium, rhodium, palladium, osmium, iridium, platinum - make them useful as active metals for catalytic reactions. Especially valuable is their property of favouring a single reaction even when the possibility of a number of parallel reactions exists under certain reaction conditions. This selectivity of the noble metal catalyst may be directed or enhanced through appropriate choise of the metal, the reaction conditions, the duration of the reaction, the amount of hydrogen etc. Even the physical state of the catalyst - supported or unsupported - is of influence when using noble metal catalysts as described in this report.

Multi-Stage Selective Catalytic Reduction of NOx in Lean-Burn Engine Exhaust

National Research Council Canada - National Science Library

Penetrante, B

1997-01-01

.... A plasma can also be used to oxidize NO to NO2. This paper compares the multi-stage catalytic scheme with the plasma-assisted catalytic scheme for reduction of NOx in lean-burn engine exhausts. The advantages of plasma oxidation over catalytic oxidation are presented.

Exhaust gas aftertreatment with online burner; Abgasnachbehandlung mit Online-Brenner

Energy Technology Data Exchange (ETDEWEB)

Rembor, Hans-Joerg; Bischler, Thomas [Huss Technologies GmbH, Nuernberg (Germany)

2010-09-15

In order to fulfil continuously tightened emission standards, modern Diesel engines for on and off road have to meet demands of catalytic exhaust gas aftertreatment with their thermomanagement. With an online burner from Huss Technologies, even with low load duty cycles, catalytic exhaust gas aftertreatment is possible. Diesel engine development can therefore be redirected again more on efficiency enhancement and other direct customer demands. (orig.)

Green technology for conversion of renewable hydrocarbon based on plasma-catalytic approach

Science.gov (United States)

Fedirchyk, Igor; Nedybaliuk, Oleg; Chernyak, Valeriy; Demchina, Valentina

2016-09-01

The ability to convert renewable biomass into fuels and chemicals is one of the most important steps on our path to green technology and sustainable development. However, the complex composition of biomass poses a major problem for established conversion technologies. The high temperature of thermochemical biomass conversion often leads to the appearance of undesirable byproducts and waste. The catalytic conversion has reduced yield and feedstock range. Plasma-catalytic reforming technology opens a new path for biomass conversion by replacing feedstock-specific catalysts with free radicals generated in the plasma. We studied the plasma-catalytic conversion of several renewable hydrocarbons using the air plasma created by rotating gliding discharge. We found that plasma-catalytic hydrocarbon conversion can be conducted at significantly lower temperatures (500 K) than during the thermochemical ( 1000 K) and catalytic (800 K) conversion. By using gas chromatography, we determined conversion products and found that conversion efficiency of plasma-catalytic conversion reaches over 85%. We used obtained data to determine the energy yield of hydrogen in case of plasma-catalytic reforming of ethanol and compared it with other plasma-based hydrogen-generating systems.

Catalytic Upgrading of Sugars to Hydrocarbons Technology Pathway

Energy Technology Data Exchange (ETDEWEB)

Biddy, M.; Jones, S.

2013-03-01

This technology pathway case investigates the catalytic conversion of solubilized carbohydrate streams to hydrocarbon biofuels, utilizing data from recent efforts within the National Advanced Biofuels Consortium (NABC) in collaboration with Virent, Inc. Technical barriers and key research needs that should be pursued for the catalytic conversion of sugars pathway to be competitive with petroleum-derived gasoline-, diesel-, and jet-range hydrocarbon blendstocks have been identified.

Janus droplet as a catalytic micromotor

Science.gov (United States)

Shklyaev, Sergey

2015-06-01

Self-propulsion of a Janus droplet in a solution of surfactant, which reacts on a half of a drop surface, is studied theoretically. The droplet acts as a catalytic motor creating a concentration gradient, which generates its surface-tension-driven motion; the self-propulsion speed is rather high, 60 μ \\text{m/s} and more. This catalytic motor has several advantages over other micromotors: simple manufacturing, easily attained neutral buoyancy. In contrast to a single-fluid droplet, which demonstrates a self-propulsion as a result of symmetry breaking instability, for the Janus one no stability threshold exists; hence, the droplet radius can be scaled down to micrometers.

Elucidation of Peptide-Directed Palladium Surface Structure for Biologically Tunable Nanocatalysts

Energy Technology Data Exchange (ETDEWEB)

Bedford, Nicholas M.; Ramezani-Dakhel, Hadi; Slocik, Joseph M.; Briggs, Beverly D.; Ren, Yang; Frenkel, Anatoly I.; Petkov, Valeri; Heinz, Hendrik; Naik, Rajesh R.; Knecht, Mark R.

2015-05-01

Peptide-enabled synthesis of inorganic nanostructures represents an avenue to access catalytic materials with tunable and optimized properties. This is achieved via peptide complexity and programmability that is missing in traditional ligands for catalytic nanomaterials. Unfortunately, there is limited information available to correlate peptide sequence to particle structure and catalytic activity to date. As such, the application of peptide-enabled nanocatalysts remains limited to trial and error approaches. In this paper, a hybrid experimental and computational approach is introduced to systematically elucidate biomolecule-dependent structure/function relationships for peptide-capped Pd nanocatalysts. Synchrotron X-ray techniques were used to uncover substantial particle surface structural disorder, which was dependent upon the amino acid sequence of the peptide capping ligand. Nanocatalyst configurations were then determined directly from experimental data using reverse Monte Carlo methods and further refined using molecular dynamics simulation, obtaining thermodynamically stable peptide-Pd nanoparticle configurations. Sequence-dependent catalytic property differences for C-C coupling and olefin hydrogenation were then eluddated by identification of the catalytic active sites at the atomic level and quantitative prediction of relative reaction rates. This hybrid methodology provides a clear route to determine peptide-dependent structure/function relationships, enabling the generation of guidelines for catalyst design through rational tailoring of peptide sequences

Heterogeneous-catalytic redox reactions in nitrate - formate systems

International Nuclear Information System (INIS)

Ananiev, A.V.; Shilov, V.P.; Tananaev, I.G.; Brossard, Ph.; Broudic, J.Ch.

2000-01-01

It was found that an intensive destruction of various organic and mineral substances - usual components of aqueous waste solutions (oxalic acid, complexones, urea, hydrazine, ammonium nitrate, etc.) takes place under the conditions of catalytic denitration. Kinetics and mechanisms of urea and ammonium nitrate decomposition in the system HNO 3 - HCOOH - Pt/SiO 2 are comprehensively investigated. The behaviour of uranium, neptunium and plutonium under the conditions of catalytic denitration is studied. It is shown, that under the certain conditions the formic acid is an effective reducer of the uranium (VI), neptunium (VI, V) and plutonium (VI, IV) ions. Kinetics of heterogeneous-catalytic red-ox reactions of uranium (VI), neptunium (VI, V) and plutonium (VI, IV) with formic acid are investigated. The mechanisms of the appropriate reactions are evaluated. (authors)

Interactions of a Pop5/Rpp1 heterodimer with the catalytic domain of RNase MRP.

Science.gov (United States)

Perederina, Anna; Khanova, Elena; Quan, Chao; Berezin, Igor; Esakova, Olga; Krasilnikov, Andrey S

2011-10-01

Ribonuclease (RNase) MRP is a multicomponent ribonucleoprotein complex closely related to RNase P. RNase MRP and eukaryotic RNase P share most of their protein components, as well as multiple features of their catalytic RNA moieties, but have distinct substrate specificities. While RNase P is practically universally found in all three domains of life, RNase MRP is essential in eukaryotes. The structural organizations of eukaryotic RNase P and RNase MRP are poorly understood. Here, we show that Pop5 and Rpp1, protein components found in both RNase P and RNase MRP, form a heterodimer that binds directly to the conserved area of the putative catalytic domain of RNase MRP RNA. The Pop5/Rpp1 binding site corresponds to the protein binding site in bacterial RNase P RNA. Structural and evolutionary roles of the Pop5/Rpp1 heterodimer in RNases P and MRP are discussed.

A Review on Direct Electrochemistry of Catalase for Electrochemical Sensors

Directory of Open Access Journals (Sweden)

Periasamy Arun Prakash

2009-03-01

Full Text Available Catalase (CAT is a heme enzyme with a Fe(III/II prosthetic group at its redox centre. CAT is present in almost all aerobic living organisms, where it catalyzes the disproportionation of H2O2 into oxygen and water without forming free radicals. In order to study this catalytic mechanism in detail, the direct electrochemistry of CAT has been investigated at various modified electrode surfaces with and without nanomaterials. The results show that CAT immobilized on nanomaterial modified electrodes shows excellent catalytic activity, high sensitivity and the lowest detection limit for H2O2 determination. In the presence of nanomaterials, the direct electron transfer between the heme group of the enzyme and the electrode surface improved significantly. Moreover, the immobilized CAT is highly biocompatible and remains extremely stable within the nanomaterial matrices. This review discusses about the versatile approaches carried out in CAT immobilization for direct electrochemistry and electrochemical sensor development aimed as efficient H2O2 determination. The benefits of immobilizing CAT in nanomaterial matrices have also been highlighted.

Catalytic flash pyrolysis of oil-impregnated-wood and jatropha cake using sodium based catalysts

NARCIS (Netherlands)

Ali Imran, A.; Bramer, Eduard A.; Seshan, Kulathuiyer; Brem, Gerrit

2016-01-01

Catalytic pyrolysis of wood with impregnated vegetable oil was investigated and compared with catalytic pyrolysis of jatropha cake making use of sodium based catalysts to produce a high quality bio-oil. The catalytic pyrolysis was carried out in two modes: in-situ catalytic pyrolysis and post

Performance simulations of catalytic converters during the Federal Test Procedure

Energy Technology Data Exchange (ETDEWEB)

Shen, H.; Shamim, T.; Sengupta, S.; Son, S.; Adamczyk, A.A.

1999-07-01

A numerical study is carried out to predict the tailpipe emissions and emission conversion efficiencies of unburned hydrocarbon, nitrogen oxide and carbon monoxide flowing through a catalytic converter during the Federal Test Procedure (FTP). The model considers the effect of heat transfer in the catalytic converter, coupled with catalyst chemical kinetics, including an oxygen storage mechanism. The resulting governing equations based on the conservation of mass and energy are solved by a tridiagonal matrix algorithm (TDMA) with a successive line under relaxation method. The numerical scheme for this non-linear problem is found to have good convergence efficiency. The simulation for the complete FTP cycle is accomplished in less than fifteen minutes on a desktop personal computer. A 13-step reaction mechanism plus a nine-step O{sub 2} storage mechanism is used to simulate the chemical kinetics. The energy equations include the heat loss due to conduction and convection plus the energy liberated by chemical reactions. The effect of radiation is assumed to be negligible and is not considered. The results of the numerical model for both the instantaneous and accumulated emissions are found to be in good agreement with experimental measurements. The conversion efficiencies of HC, CO and NO as predicted by the model are found to be within 5% of those dynamic measurements, and calculated results of accumulated HC, CO and NO{sub x} are in fair agreement with experimental measurements. The transient measurements are also used to check the robustness of the numerical model. The model is found to be robust and hence can simulate various operating conditions of engine output to the converter.

Insights into the Functions of a Prophage Recombination Directionality Factor

Directory of Open Access Journals (Sweden)

Mireille Ansaldi

2012-10-01

Full Text Available Recombination directionality factors (RDFs, or excisionases, are essential players of prophage excisive recombination. Despite the essentially catalytic role of the integrase in both integrative and excisive recombination, RDFs are required to direct the reaction towards excision and to prevent re-integration of the prophage genome when entering a lytic cycle. KplE1, HK620 and numerous (prophages that integrate at the same site in enterobacteria genomes (such as the argW tRNA gene all share a highly conserved recombination module. This module comprises the attL and attR recombination sites and the RDF and integrase genes. The KplE1 RDF was named TorI after its initial identification as a negative regulator of the tor operon. However, it was characterized as an essential factor of excisive recombination. In this study, we designed an extensive random mutagenesis protocol of the torI gene and identified key residues involved in both functions of the TorI protein. We show that, in addition to TorI-TorR protein-protein interaction, TorI interacts in solution with the IntS integrase. Moreover, in vitro, TorR and IntS appear to compete for TorI binding. Finally, our mutagenesis results suggest that the C-terminal part of the TorI protein is dedicated to protein-protein interactions with both proteins TorR and IntS.

Millisecond dynamics in glutaredoxin during catalytic turnover is dependent on substrate binding and absent in the resting states

DEFF Research Database (Denmark)

Jensen, Kristine Steen; Winther, Jakob R; Teilum, Kaare

2011-01-01

to the glutathione exchange rate was observed for 23 residues. Binding of reduced glutathione resulted in competitive inhibition of the reduced enzyme having kinetics similar to that of the reaction. This observation couples the motions observed during catalysis directly to substrate binding. Backbone motions......Conformational dynamics is important for enzyme function. Which motions of enzymes determine catalytic efficiency and whether the same motions are important for all enzymes, however, are not well understood. Here we address conformational dynamics in glutaredoxin during catalytic turnover...... with a combination of NMR magnetization transfer, R(2) relaxation dispersion, and ligand titration experiments. Glutaredoxins catalyze a glutathione exchange reaction, forming a stable glutathinoylated enzyme intermediate. The equilibrium between the reduced state and the glutathionylated state was biochemically...

Pyroelectric Energy Harvesting: With Thermodynamic-Based Cycles

OpenAIRE

Saber Mohammadi; Akram Khodayari

2012-01-01

This work deals with energy harvesting from temperature variations using ferroelectric materials as a microgenerator. The previous researches show that direct pyroelectric energy harvesting is not effective, whereas thermodynamic-based cycles give higher energy. Also, at different temperatures some thermodynamic cycles exhibit different behaviours. In this paper pyroelectric energy harvesting using Lenoir and Ericsson thermodynamic cycles has been studied numerically and the two cycles were c...

HTGR fuel and fuel cycle technology

International Nuclear Information System (INIS)

Lotts, A.L.; Coobs, J.H.

1976-08-01

The status of fuel and fuel cycle technology for high-temperature gas-cooled reactors (HTGRs) is reviewed. The all-ceramic core of the HTGRs permits high temperatures compared with other reactors. Core outlet temperatures of 740 0 C are now available for the steam cycle. For advanced HTGRs such as are required for direct-cycle power generation and for high-temperature process heat, coolant temperatures as high as 1000 0 C may be expected. The paper discusses the variations of HTGR fuel designs that meet the performance requirements and the requirements of the isotopes to be used in the fuel cycle. Also discussed are the fuel cycle possibilities, which include the low-enrichment cycle, the Th- 233 U cycle, and plutonium utilization in either cycle. The status of fuel and fuel cycle development is summarized

On the Pt(+) and Rh(+) Catalytic Activity in the Nitrous Oxide Reduction by Carbon Monoxide.

Science.gov (United States)

Rondinelli, F; Russo, N; Toscano, M

2008-11-11

Nitrous oxide activation by CO in the presence of platinum and rhodium monocations was elucidated by density functional methods for ground and first excited states. Platinum and rhodium cations fulfill the thermodynamic request for the oxygen-atom transport that allows the catalytic cycle to be completed, but actually, just the first one meaningfully improves the kinetics of the process. For both catalysts, the reaction pathways show the only activation barrier in correspondence of nitrogen release and monoxide cation formation. The kinetic analysis of the potential energy profile, in agreement with ICP/SIFT MS experimental data, indicates that platinum performs more in the reduction, while the whole process is not sufficiently fast in the case of rhodium ionic catalyst.

Catalytic copyrolysis of cork oak and bio-oil distillation residue

Science.gov (United States)

Lee, Yejin; Oh, Daejun; Kim, Young-Min; Jae, Jungho; Jung, Sang-Chul; Jeon, Jong-Ki; Kim, Sang Chai; Park, Young-Kwon

2018-01-01

The atmospheric distillation residue (ADR) of cork oak (CO) pyrolysis oil was used as the co-feeding material for the catalytic pyrolysis of CO over HZSM-5 catalysts to improve the formation of aromatic hydrocarbons. Although the non-catalytic copyrolysis of CO and ADR did not improve the formation of aromatic hydrocarbons, the catalytic copyrolysis of CO and ADR promoted the synergistic formation of aromatic hydrocarbons. HZSM-5(30), having a lower SiO2/Al2O3(30), showed better performance for the formation of aromatic hydrocarbons than HZSM-5(80) because of its higher acidity. The catalytic copyrolysis of CO and ADR also decreased the formation of coke. The largest quantity of aromatic hydrocarbons was obtained from the catalytic copyrolysis of CO and ADR over HZSM-5 (30) at 600 °C, whereas the lowest coke yield was achieved at 700 °C. When the catalyst to sample ratio was increased from 2:1 to 5:1, the synergistic formation of aromatic hydrocarbons was limited, resulting in a lower experimental yield of aromatic hydrocarbons than the theoretical yield. A lower coke yield was also achieved at a high catalyst to sample ratio (5:1).

Life Cycle Assessment of Thermal Treatment Technologies. An environmental and financial systems analysis of gasification, incineration and landfilling of waste

Energy Technology Data Exchange (ETDEWEB)

Assefa, Getachew; Eriksson, Ola [Royal Inst. of Tech., Stockholm (Sweden). Industrial Ecology; Jaeraas, Sven; Kusar, Henrik [Royal Inst. of Tech., Stockholm (Sweden). Chemical Technology

2003-05-01

A technology which is currently developed by researchers at KTH is catalytic combustion. which is one component of a gasification system. Instead of performing the combustion in the gas turbine by a flame, a catalyst is used. When the development of a new technology (as catalytic combustion) reaches a certain step where it is possible to quantify material-, energy- and capital flows, the prerequisites for performing a systems analysis is at hand. The systems analysis can be used to expand the know-how about the potential advantages of the catalytic combustion technology by highlighting its function as a component of a larger system. In this way it may be possible to point out weak points which have to be investigated more, but also strong points to emphasise the importance of further development. The aim of this project was to assess the energy turnover as well as the potential environmental impacts and economic costs of thermal treatment technologies in general and catalytic combustion in particular. By using a holistic assessment of the advantages and disadvantages of catalytic combustion of waste it was possible to identify the strengths and weaknesses of the technology under different conditions. Following different treatment scenarios have been studied: (1) Gasification with catalytic combustion, (2) Gasification with flame combustion, (3) Incineration with energy recovery and (4) Landfilling with gas collection. In the study compensatory district heating is produced by combustion. of biofuel. The power used for running the processes in the scenarios is supplied by the waste-to-energy technologies themselves while compensatory power is assumed to be produced. from natural gas. The emissions from the system studied were classified and characterised using methodology from Life Cycle Assessment into the following environmental impact categories: Global Warming Potential, Acidification Potential, Eutrophication Potential and finally Formation of Photochemical

Studies of coupled chemical and catalytic coal conversion methods

Energy Technology Data Exchange (ETDEWEB)

Stock, L.M.

1990-01-01

This report concerns our research on base-catalyzed coal solubilization and a new approach for hydrogen addition. The work on base-catalyzed, chemical solubilization is continuing. this report is focused on the hydrogenation research. Specifically it deals with the use of arene chromium carbonyl complexes as reagents for the addition of dideuterium to coal molecules. In one phase of the work, he has established that the aromatic hydrocarbons in a representative coal liquid can be converted in very good yield to arene chromium carbonyl compounds. In a second phase of the work directly related to our objective of improved methods for catalytic hydrogenation, he has established that the aromatic constituents of the same coal liquid add dideuterium in the presence of added napththalene chromium carbonyl.

Facile synthesis of pristine graphene-palladium nanocomposites with extraordinary catalytic activities using swollen liquid crystals

Science.gov (United States)

Vats, T.; Dutt, S.; Kumar, R.; Siril, P. F.

2016-09-01

Amazing conductivity, perfect honeycomb sp2 arrangement and the high theoretical surface area make pristine graphene as one of the best materials suited for application as catalyst supports. Unfortunately, the low reactivity of the material makes the formation of nanocomposite with inorganic materials difficult. Here we report an easy approach to synthesize nanocomposites of pristine graphene with palladium (Pd-G) using swollen liquid crystals (SLCs) as a soft template. The SLC template gives the control to deposit very small Pd particles of uniform size on G as well as RGO. The synthesized nanocomposite (Pd-G) exhibited exceptionally better catalytic activity compared with Pd-RGO nanocomposite in the hydrogenation of nitrophenols and microwave assisted C-C coupling reactions. The catalytic activity of Pd-G nanocomposite during nitrophenol reduction reaction was sixteen times higher than Pd nanoparticles and more than double than Pd-RGO nanocomposite. The exceptionally high activity of pristine graphene supported catalysts in the organic reactions is explained on the basis of its better pi interacting property compared to partially reduced RGO. The Pd-G nanocomposite showed exceptional stability under the reaction conditions as it could be recycled upto a minimum of 15 cycles for the C-C coupling reactions without any loss in activity.

Thermal and catalytic pyrolysis of plastic waste

Directory of Open Access Journals (Sweden)

Débora Almeida

2016-02-01

Full Text Available Abstract The amount of plastic waste is growing every year and with that comes an environmental concern regarding this problem. Pyrolysis as a tertiary recycling process is presented as a solution. Pyrolysis can be thermal or catalytical and can be performed under different experimental conditions. These conditions affect the type and amount of product obtained. With the pyrolysis process, products can be obtained with high added value, such as fuel oils and feedstock for new products. Zeolites can be used as catalysts in catalytic pyrolysis and influence the final products obtained.

Using electron beams to investigate catalytic materials

International Nuclear Information System (INIS)

Zhang, Bingsen; Su, Dang Sheng

2014-01-01

Transmission Electron microscopy (TEM) enables us, not only to reveal the morphology, but also to provide structural, chemical and electronic information about solid catalysts at the atomic level, providing a dramatic driving force for the development of heterogeneous catalysis. Almost all catalytic materials have been studied with TEM in order to obtain information about their structures, which can help us to establish the synthesis-structure-property relationships and to design catalysts with new structures and desired properties. Herein, several examples will be reviewed to illustrate the investigation of catalytic materials by using electron beams. (authors)

Stable cycling in discrete-time genetic models.

OpenAIRE

Hastings, A

1981-01-01

Examples of stable cycling are discussed for two-locus, two-allele, deterministic, discrete-time models with constant fitnesses. The cases that cycle were found by using numerical techniques to search for stable Hopf bifurcations. One consequence of the results is that apparent cases of directional selection may be due to stable cycling.

Stable cycling in discrete-time genetic models.

Science.gov (United States)

Hastings, A

1981-11-01

Examples of stable cycling are discussed for two-locus, two-allele, deterministic, discrete-time models with constant fitnesses. The cases that cycle were found by using numerical techniques to search for stable Hopf bifurcations. One consequence of the results is that apparent cases of directional selection may be due to stable cycling.

Engineering reactors for catalytic reactions

Indian Academy of Sciences (India)

126, No. 2, March 2014, pp. 341–351. c Indian Academy of Sciences. ... enhancement was realized by catalyst design, appropriate choice of reactor, better injection and .... Gas–liquid and liquid–solid transport processes in catalytic reactors.5.

Catalytic effect of light illumination on bioleaching of chalcopyrite.

Science.gov (United States)

Zhou, Shuang; Gan, Min; Zhu, Jianyu; Li, Qian; Jie, Shiqi; Yang, Baojun; Liu, Xueduan

2015-04-01

The influence of visible light exposure on chalcopyrite bioleaching was investigated using Acidithiobacillus ferrooxidans. The results indicated, in both shake-flasks and aerated reactors with 8500-lux light, the dissolved Cu was 91.80% and 23.71% higher, respectively, than that in the controls without light. The catalytic effect was found to increase bioleaching to a certain limit, then plateaued as the initial chalcopyrite concentration increased from 2% to 4.5%. Thus a balanced mineral concentration is highly amenable to bioleaching via offering increased available active sites for light adsorption while eschewing mineral aggregation and screening effects. Using semiconducting chalcopyrite, the light facilitated the reduction of Fe(3+) to Fe(2+) as metabolic substrates for A.ferrooxidans, leading to better biomass, lower pH and redox potential, which are conducive to chalcopyrite leaching. The light exposure on iron redox cycling was further confirmed by chemical leaching tests using Fe(3+), which exhibited higher Fe(2+) levels in the light-induced system. Copyright © 2015 Elsevier Ltd. All rights reserved.

Three dimensional graphene foam supported platinum-ruthenium bimetallic nanocatalysts for direct methanol and direct ethanol fuel cell applications

Science.gov (United States)

Kung, Chih-Chien; Lin, Po-Yuan; Xue, Yuhua; Akolkar, Rohan; Dai, Liming; Yu, Xiong; Liu, Chung-Chiun

2014-06-01

A novel composite material of hierarchically structured platinum-ruthenium (PtRu) nanoparticles grown on large surface area three dimensional graphene foam (3D GF) is reported. 3D GF was incorporated with PtRu bimetallic nanoparticles as an electrochemical nanocatalyst for methanol and ethanol oxidation. PtRu/3D GF nanocatalyst showed a higher tolerance to poisoning by CO and exhibited improved catalytic activity for both methanol oxidation reaction (MOR) and ethanol oxidation reaction (EOR). Cyclic voltammetry (CV) results and long-term cycling stability tests demonstrated that GF provided a promising platform for the development of electrochemical nanocatalysts. Specifically, PtRu/3D GF nanocatalyst showed excellent catalytic activity toward MOR and EOR compared with PtRu/Graphene (Commercial graphene), PtRu/C (Vulcan XC-72R carbon), and PtRu alone. The crystal size of PtRu on 3D GF was reduced to 3.5 nm and its active surface area was enhanced to 186.2 m2 g-1. Consequently, the MOR and EOR rates were nearly doubled on PtRu/3D GF compared to those on PtRu/Graphene.

Materials for High-Temperature Catalytic Combustion

Energy Technology Data Exchange (ETDEWEB)

Ersson, Anders

2003-04-01

Catalytic combustion is an environmentally friendly technique to combust fuels in e.g. gas turbines. Introducing a catalyst into the combustion chamber of a gas turbine allows combustion outside the normal flammability limits. Hence, the adiabatic flame temperature may be lowered below the threshold temperature for thermal NO{sub X} formation while maintaining a stable combustion. However, several challenges are connected to the application of catalytic combustion in gas turbines. The first part of this thesis reviews the use of catalytic combustion in gas turbines. The influence of the fuel has been studied and compared over different catalyst materials. The material section is divided into two parts. The first concerns bimetallic palladium catalysts. These catalysts showed a more stable activity compared to their pure palladium counterparts for methane combustion. This was verified both by using an annular reactor at ambient pressure and a pilot-scale reactor at elevated pressures and flows closely resembling the ones found in a gas turbine combustor. The second part concerns high-temperature materials, which may be used either as active or washcoat materials. A novel group of materials for catalysis, i.e. garnets, has been synthesised and tested in combustion of methane, a low-heating value gas and diesel fuel. The garnets showed some interesting abilities especially for combustion of low-heating value, LHV, gas. Two other materials were also studied, i.e. spinels and hexa aluminates, both showed very promising thermal stability and the substituted hexa aluminates also showed a good catalytic activity. Finally, deactivation of the catalyst materials was studied. In this part the sulphur poisoning of palladium, platinum and the above-mentioned complex metal oxides has been studied for combustion of a LHV gas. Platinum and surprisingly the garnet were least deactivated. Palladium was severely affected for methane combustion while the other washcoat materials were

Environmental macroeconomics : Environmental policy, business cycles, and directed technical change

NARCIS (Netherlands)

Fischer, Carolyn; Heutel, Garth

Environmental economics has traditionally fallen in the domain of microeconomics, but approaches from macroeconomics have recently been applied to studying environmental policy. We focus on two macroeconomic tools and their application to environmental economics. First, real-business-cycle models

Combined hydrothermal liquefaction and catalytic hydrothermal gasification system and process for conversion of biomass feedstocks

Science.gov (United States)

Elliott, Douglas C.; Neuenschwander, Gary G.; Hart, Todd R.

2017-09-12

A combined hydrothermal liquefaction (HTL) and catalytic hydrothermal gasification (CHG) system and process are described that convert various biomass-containing sources into separable bio-oils and aqueous effluents that contain residual organics. Bio-oils may be converted to useful bio-based fuels and other chemical feedstocks. Residual organics in HTL aqueous effluents may be gasified and converted into medium-BTU product gases and directly used for process heating or to provide energy.

Small-Sized Mg–Al LDH Nanosheets Supported on Silica Aerogel with Large Pore Channels: Textural Properties and Basic Catalytic Performance after Activation

Directory of Open Access Journals (Sweden)

Lijun Wang

2018-02-01

Full Text Available Layered double hydroxides (LDHs have been widely used as an important subset of solid base catalysts. However, developing low-cost, small-sized LDH nanoparticles with enhanced surface catalytic sites remains a challenge. In this work, silica aerogel (SA-supported, small-sized Mg–Al LDH nanosheets were successfully prepared by one-pot coprecipitation of Mg and Al ions in an alkaline suspension of crushed silica aerogel. The supported LDH nanosheets were uniformly dispersed in the SA substrate with the smallest average radial diameter of 19.2 nm and the thinnest average thickness of 3.2 nm, both dimensions being significantly less than those of the vast majority of LDH nanoparticles reported. The SA/LDH composites also showed large pore volume (up to 1.3 cm3·g and pore diameter (>9 nm, and therefore allow efficient access of reactants to the edge catalytic sites of LDH nanosheets. In a base-catalyzed Henry reaction of benzaldehyde with nitromethane, the SA/LDH catalysts showed high reactant conversions and favorable stability in 6 successive cycles of reactions. The low cost of the SA carrier and LDH precursors, easy preparation method, and excellent catalytic properties make these SA/LDH composites a competitive example of solid-base catalysts.

Catalytic enantioselective Reformatsky reaction with ketones

NARCIS (Netherlands)

Fernandez-Ibanez, M. Angeles; Macia, Beatriz; Minnaard, Adriaan J.; Feringa, Ben L.

2008-01-01

Chiral tertiary alcohols were obtained with good yields and enantioselectivities via a catalytic Reformatsky reaction with ketones, including the challenging diaryl ketones, using chiral BINOL derivatives.

Catalytic dehydration of ethanol using transition metal oxide catalysts.

Science.gov (United States)

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.

Closed-Cycle, Frequency-Stable CO2 Laser Technology

Science.gov (United States)

Batten, Carmen E. (Editor); Miller, Irvin M. (Editor); Wood, George M., Jr. (Editor); Willetts, David V. (Editor)

1987-01-01

These proceedings contain a collection of papers and comments presented at a workshop on technology associated with long-duration closed-cycle operation of frequency-stable, pulsed carbon dioxide lasers. This workshop was held at the NASA Langley Research Center June 10 to 12, 1986. The workshop, jointly sponsored by the National Aeronautics and Space Administration (NASA) and the Royal Signals and Radar Establishment (RSRE), was attended by 63 engineers and scientists from the United States and the United Kingdom. During the 2 1/2 days of the workshop, a number of issues relating to obtaining frequency-stable operation and to the catalytic control of laser gas chemistry were discussed, and specific recommendations concerning future activities were drafted.

Novel Catalytic Membrane Reactors

Energy Technology Data Exchange (ETDEWEB)

Stuart Nemser, PhD

2010-10-01

There are many industrial catalytic organic reversible reactions with amines or alcohols that have water as one of the products. Many of these reactions are homogeneously catalyzed. In all cases removal of water facilitates the reaction and produces more of the desired chemical product. By shifting the reaction to right we produce more chemical product with little or no additional capital investment. Many of these reactions can also relate to bioprocesses. Given the large number of water-organic compound separations achievable and the ability of the Compact Membrane Systems, Inc. (CMS) perfluoro membranes to withstand these harsh operating conditions, this is an ideal demonstration system for the water-of-reaction removal using a membrane reactor. Enhanced reaction synthesis is consistent with the DOE objective to lower the energy intensity of U.S. industry 25% by 2017 in accord with the Energy Policy Act of 2005 and to improve the United States manufacturing competitiveness. The objective of this program is to develop the platform technology for enhancing homogeneous catalytic chemical syntheses.

Catalyst engineering for lithium ion batteries: the catalytic role of Ge in enhancing the electrochemical performance of SnO2(GeO2)0.13/G anodes.

Science.gov (United States)

Zhu, Yun Guang; Wang, Ye; Han, Zhao Jun; Shi, Yumeng; Wong, Jen It; Huang, Zhi Xiang; Ostrikov, Kostya Ken; Yang, Hui Ying

2014-12-21

The catalytic role of germanium (Ge) was investigated to improve the electrochemical performance of tin dioxide grown on graphene (SnO(2)/G) nanocomposites as an anode material of lithium ion batteries (LIBs). Germanium dioxide (GeO(20) and SnO(2) nanoparticles (GeO(2))0.13/G nanocomposites can deliver a capacity of 1200 mA h g(-1) at a current density of 100 mA g(-1), which is much higher than the traditional theoretical specific capacity of such nanocomposites (∼ 702 mA h g(-1)). More importantly, the SnO(2)(GeO(2))0.13/G nanocomposites exhibited an improved rate, large current capability (885 mA h g(-1) at a discharge current of 2000 mA g(-1)) and excellent long cycling stability (almost 100% retention after 600 cycles). The enhanced electrochemical performance was attributed to the catalytic effect of Ge, which enabled the reversible reaction of metals (Sn and Ge) to metals oxide (SnO(2) and GeO(2)) during the charge/discharge processes. Our demonstrated approach towards nanocomposite catalyst engineering opens new avenues for next-generation high-performance rechargeable Li-ion batteries anode materials.

Catalytic Reactor for Inerting of Aircraft Fuel Tanks

Science.gov (United States)

1974-06-01

Aluminum Panels After Triphase Corrosion Test 79 35 Inerting System Flows in Various Flight Modes 82 36 High Flow Reactor Parametric Data 84 37 System...AD/A-000 939 CATALYTIC REACTOR FOR INERTING OF AIRCRAFT FUEL TANKS George H. McDonald, et al AiResearch Manufacturing Company Prepared for: Air Force...190th Street 2b. GROUP Torrance, California .. REPORT TITLE CATALYTIC REACTOR FOR INERTING OF AIRCRAFT FUEL TANKS . OESCRIP TIVE NOTEs (Thpe of refpoft

Aerobic, catalytic oxidation of alcohols in ionic liquids

Directory of Open Access Journals (Sweden)

Souza Roberto F. de

2006-01-01

Full Text Available An efficient and simple catalytic system based on RuCl3 dissolved in ionic liquids has been developed for the oxidation of alcohols into aldehydes and ketones under mild conditions. A new fluorinated ionic liquid, 1-n-butyl-3-methylimidazolium pentadecafluorooctanoate, was synthesized and demonstrated better performance that the other ionic liquids employed. Moreover this catalytic system utilizes molecular oxygen as an oxidizing agent, producing water as the only by-product.

Catalytic soman scavenging by Y337A/F338A acetylcholinesterase mutant assisted with novel site-directed aldoximes

Science.gov (United States)

Kovarik, Zrinka; Hrvat, Nikolina Maček; Katalinić, Maja; Sit, Rakesh K.; Paradyse, Alexander; Žunec, Suzana; Musilek, Kamil; Fokin, Valery V.; Taylor, Palmer; Radić, Zoran

2016-01-01

Exposure to the nerve agent soman is difficult to treat due to the rapid dealkylation of soman-acetylcholinesterase (AChE) conjugate known as aging. Oxime antidotes commonly used to reactivate organophosphate inhibited AChE are ineffective against soman, while the efficacy of the recommended nerve agent bioscavenger butyrylcholinesterase is limited by strictly stoichiometric scavenging. To overcome this limitation, we tested ex vivo, in human blood, and in vivo, in soman exposed mice, the capacity of aging-resistant human AChE mutant Y337A/F338A in combination with oxime HI-6 to act as a catalytic bioscavenger of soman. HI-6 was previously shown in vitro to efficiently reactivate this mutant upon soman, as well as VX, cyclosarin, sarin and paraoxon inhibition. We here demonstrate that ex vivo, in whole human blood, 1 μM soman was detoxified within 30 minutes when supplemented with 0.5 μM Y337A/F338A AChE and 100 μM HI-6. This combination was further tested in vivo. Catalytic scavenging of soman in mice improved the therapeutic outcome and resulted in the delayed onset of toxicity symptoms. Furthermore, in a preliminary in vitro screen we identified an even more efficacious oxime than HI-6, in a series of forty-two pyridinium aldoximes, and five imidazole 2-aldoxime N-propyl pyridinium derivatives. One of the later imidazole aldoximes, RS-170B, was a 2–3 –fold more effective reactivator of Y337A/F338A AChE than HI-6 due to the smaller imidazole ring, as indicated by computational molecular models, that affords a more productive angle of nucleophilic attack. PMID:25835984

Catalytic applications of bio-inspired nanomaterials

Science.gov (United States)

Pacardo, Dennis Kien Balaong

The biomimetic synthesis of Pd nanoparticles was presented using the Pd4 peptide, TSNAVHPTLRHL, isolated from combinatorial phage display library. Using this approach, nearly monodisperse and spherical Pd nanoparticles were generated with an average diameter of 1.9 +/- 0.4 nm. The peptide-based nanocatalyst were employed in the Stille coupling reaction under energy-efficient and environmentally friendly reaction conditions of aqueous solvent, room temperature and very low catalyst loading. To this end, the Pd nanocatalyst generated high turnover frequency (TOF) value and quantitative yields using ≥ 0.005 mol% Pd as well as catalytic activities with different aryl halides containing electron-withdrawing and electron-donating groups. The Pd4-capped Pd nanoparticles followed the atom-leaching mechanism and were found to be selective with respect to substrate identity. On the other hand, the naturally-occurring R5 peptide (SSKKSGSYSGSKGSKRRIL) was employed in the synthesis of biotemplated Pd nanomaterials which showed morphological changes as a function of Pd:peptide ratio. TOF analysis for hydrogenation of olefinic alcohols showed similar catalytic activity regardless of nanomorphology. Determination of catalytic properties of these bio-inspired nanomaterials are important as they serve as model system for alternative green catalyst with applications in industrially important transformations.

Cycling environmental perception in Beijing – A study of residents' attitudes towards future cycling and car purchasing

DEFF Research Database (Denmark)

Zhao, Chunli; Nielsen, Thomas Alexander Sick; Olafsson, Anton Stahl

2018-01-01

distances up to 2 km are positively linked to future cycling prospects. Non-car owners' attitude to future car ownership is strongly linked to socio-demographic status - low education and low income level groups seems to be most unlikely to take up driving in the future. To encourage people to cycle more...... and drive less, policy should direct efforts to promoting the clarity of cycling space on the street and strengthen pro-cycling policies. Attention should also be given to stabilizing the current travel modes of non-car users, including promoting the image of cycling, improving the service of walking...

Air bottoming cycle, an alternative to combined cycles. Final report

Energy Technology Data Exchange (ETDEWEB)

Kaikko, J. [Royal Inst. of Techn., Stockholm (Sweden). Dept. of Energy Technology

2001-10-01

directly for industrial purposes. Furthermore, the ABC can be split on the compression side and part of the flow can be directed to a reversed Brayton cycle producing cold air. The cold airflow can in turn be used for air conditioning or industrial duties. The idea of a trigenerative ABC (TriABC) is presented in the report. An ABC concept producing electricity, heat and cold in small-scale installation, can be an attractive alternative for local power production. Environmental advantages, as reduced CO2 emission and CFC-free heat pump, should be recognised. To explore the expected potential of the ABC and TriABC, it is necessary to conduct a feasibility study among the Swedish municipalities and industries. The design of the resulting specified ABC/TriABC system can be best performed in co-operation with gas turbine manufacturers.

New insights into the catalytic mechanism of Bombyx mori prostaglandin E synthase gained from structure–function analysis

Energy Technology Data Exchange (ETDEWEB)

Yamamoto, Kohji, E-mail: yamamok@agr.kyushu-u.ac.jp [Faculty of Agriculture, Kyushu University Graduate School, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581 (Japan); Suzuki, Mamoru; Higashiura, Akifumi [Institute for Protein Research, Osaka University, Suita 565-0871 (Japan); Aritake, Kosuke; Urade, Yoshihiro; Uodome, Nobuko [Department of Molecular Behavioral Biology, Osaka Bioscience Institute, 6-2-4 Furuedai, Suita, Osaka 565-0874 (Japan); Hossain, MD. Tofazzal [Faculty of Agriculture, Kyushu University Graduate School, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581 (Japan); Nakagawa, Atsushi [Institute for Protein Research, Osaka University, Suita 565-0871 (Japan)

2013-11-01

Highlights: •Structure of Bombyx mori prostaglandin E synthase is determined. •Bound glutathione sulfonic acid is located at the glutathione-binding site. •Electron-sharing network is present in this protein. •This network includes Asn95, Asp96, and Arg98. •Site-directed mutagenesis reveals that the residues contribute to the catalytic activity. -- Abstract: Prostaglandin E synthase (PGES) catalyzes the isomerization of PGH{sub 2} to PGE{sub 2}. We previously reported the identification and structural characterization of Bombyx mori PGES (bmPGES), which belongs to Sigma-class glutathione transferase. Here, we extend these studies by determining the structure of bmPGES in complex with glutathione sulfonic acid (GTS) at a resolution of 1.37 Å using X-ray crystallography. GTS localized to the glutathione-binding site. We found that electron-sharing network of bmPGES includes Asn95, Asp96, and Arg98. Site-directed mutagenesis of these residues to create mutant forms of bmPGES mutants indicate that they contribute to catalytic activity. These results are, to our knowledge, the first to reveal the presence of an electron-sharing network in bmPGES.

Simulation on Toxic Gases in Vehicle Exhaust Equipped with Modified Catalytic Converter : A Review

Directory of Open Access Journals (Sweden)

Leman A.M.

2016-01-01

Full Text Available Air pollution and global warming is a major issue nowadays. One of the main contributors to be the emission of harmful gases produced by vehicle exhausts lines. The harmful gases like NOx, CO, unburned HC and particulate matter increases the global warming, so catalytic converter plays a vital role in reducing harmful gases. Catalytic converters are used on most vehicles on the road today. This research deals with the gas emission flow in the catalytic converter involving the heat transfer, velocity flow, back pressure and others chemical reaction in the modified catalytic converter by using FeCrAl as a substrate that is treated using the ultrasonic bath and electroplating techniques. The objective of this study is to obtain a quantitative description of the gas emission in the catalytic converter system of automobile exhaust gas using ANSYS Software. The description of the gas emission in the catalytic converter system of automobile exhaust gas using ANSYS Software was simulated in this research in order to provide better efficiency and ease the reusability of the catalytic converter by comparing experimental data with software analysing data. The result will be expected to demonstrate a good approximation of gas emission in the modified catalytic converter simulation data compared to experimental data in order to verify the effectiveness of modified catalytic converter. Therefore studies on simulation of flow through the modified catalytic converter are very important to increase the accuracy of the obtained emission result.

Ionic Liquids: The Synergistic Catalytic Effect in the Synthesis of Cyclic Carbonates

Directory of Open Access Journals (Sweden)

Flora T.T. Ng

2013-10-01

Full Text Available This review presents the synergistic effect in the catalytic system of ionic liquids (ILs for the synthesis of cyclic carbonate from carbon dioxide and epoxide. The emphasis of this review is on three aspects: the catalytic system of metal-based ionic liquids, the catalytic system of hydrogen bond-promoted ionic liquids and supported ionic liquids. Metal and ionic liquids show a synergistic effect on the cycloaddition reactions of epoxides. The cations and anions of ionic liquids show a synergistic effect on the cycloaddition reactions. The functional groups in cations or supports combined with the anions have a synergistic effect on the cycloaddition reactions. Synergistic catalytic effects of ILs play an important role of promoting the cycloaddition reactions of epoxides. The design of catalytic system of ionic liquids will be possible if the synergistic effect on a molecular level is understood.

Oscillatory behaviour of catalytic properties, structure and temperature during the catalytic partial oxidation of methane on Pd/Al2O3

DEFF Research Database (Denmark)

Kimmerle, B.; Baiker, A.; Grunwaldt, Jan-Dierk

2010-01-01

Pd/Al2O3 catalysts showed an oscillatory behaviour during the catalytic partial oxidation (CPO) of methane, which was investigated simultaneously by IR-thermography, X-ray absorption spectroscopy, and online mass-spectrometry to correlate the temperature, state of the catalyst and catalytic...... to self-reduction leading to extinction of the process. The latter was the key driver for the oscillations and thus gave additional insight into the mechanism of partial methane oxidation....

DIRECT FORMATION OF TETRAHYDROPYRANOLS VIA CATALYSIS IN IONIC LIQUID. (R828129)

Science.gov (United States)

Utilizing a simple homoallyl alcohol and an aldehyde in the presence of a catalytic amount of cerium triflate, the direct stereoselective formation of tetrahydropyranol derivatives in ionic liquid is reported.

Back-end of the nuclear fuel cycle

International Nuclear Information System (INIS)

Choi, J.S.

2002-01-01

Current strategies of the back-end nuclear fuel cycles are: (1) direct-disposal of spent fuel (Open Cycle), and (2) reprocessing of the spent fuel and recycling of the recovered nuclear materials (Closed Cycle). The selection of these strategies is country-specific, and factors affecting selection of strategy are identified and discussed in this paper. (author)

Scenario uncertainties in estimating direct land-use change emissions in biomass-to-energy life cycle assessment

International Nuclear Information System (INIS)

Curtright, Aimee E.; Johnson, David R.; Willis, Henry H.; Skone, Timothy

2012-01-01

The use of biomass for energy production has increasingly been encouraged in the United States, in part motivated by the potential to reduce greenhouse gas (GHG) emissions relative to fossil fuels. However, the GHG-intensity of biomass-derived energy is highly dependent on how the biomass is obtained and used. We explore scenario uncertainty in GHG estimates in the Calculating Uncertainty in Biomass Emissions (CUBE) model and find that direct land-use change emissions that result during the biomass production often dominate the total “farm-to-hopper” GHGs. CUBE represents each land-use change decision as a conversion of land from one of four specified baseline ecosystem to produce one of seven feedstock crops, both distinct by geographic region, and then determines the implied changes in soil organic carbon, root carbon, and above-ground biomass. CUBE therefore synthesizes and organizes the existing literature to represent direct land-use change emissions in a way that can be more readily incorporated into life cycle assessment. Our approach to representing direct land-use change literature has been applied to a specific set of data and offers immediate implications for decisionmakers, but it can also be generalized and replicated in the future, making use of improved scientific data on the magnitude and rates of direct land-use change emissions as it becomes available. -- Highlights: ► The GHG-intensity of bioenergy depends on how the biomass is obtained and used. ► Total GHG emissions may be dominated by direct land-use change emissions. ► There is significant scenario uncertainty in emissions based on the location of production. ► Emissions vary based on time elapsed since land-use change conversions. ► Our approach can be generalized to use improved scientific data in the future.

Methods of using structures including catalytic materials disposed within porous zeolite materials to synthesize hydrocarbons

Science.gov (United States)

Rollins, Harry W [Idaho Falls, ID; Petkovic, Lucia M [Idaho Falls, ID; Ginosar, Daniel M [Idaho Falls, ID

2011-02-01

Catalytic structures include a catalytic material disposed within a zeolite material. The catalytic material may be capable of catalyzing a formation of methanol from carbon monoxide and/or carbon dioxide, and the zeolite material may be capable of catalyzing a formation of hydrocarbon molecules from methanol. The catalytic material may include copper and zinc oxide. The zeolite material may include a first plurality of pores substantially defined by a crystal structure of the zeolite material and a second plurality of pores dispersed throughout the zeolite material. Systems for synthesizing hydrocarbon molecules also include catalytic structures. Methods for synthesizing hydrocarbon molecules include contacting hydrogen and at least one of carbon monoxide and carbon dioxide with such catalytic structures. Catalytic structures are fabricated by forming a zeolite material at least partially around a template structure, removing the template structure, and introducing a catalytic material into the zeolite material.

Surface composition of carburized tungsten trioxide and its catalytic activity

International Nuclear Information System (INIS)

Nakazawa, M.; Okamoto, H.

1985-01-01

The surface composition and electronic structure of carburized tungsten trioxide are investigated using x-ray photoelectron spectroscopy (XPS). The relationship between the surface composition and the catalytic activity for methanol electro-oxidation is clarified. The tungsten carbide concentration in the surface layer increases with the carburization time. The formation of tungsten carbide enhances the catalytic activity. On the other hand, the presence of free carbon or tungsten trioxide in the surface layer reduces the activity remarkably. It is also shown that, the higher the electronic density of states near the Fermi level, the higher the catalytic activity

Poisoning of bubble propelled catalytic micromotors: the chemical environment matters.

Science.gov (United States)

Zhao, Guanjia; Sanchez, Samuel; Schmidt, Oliver G; Pumera, Martin

2013-04-07

Self-propelled catalytic microjets have attracted considerable attention in recent years and these devices have exhibited the ability to move in complex media. The mechanism of propulsion is via the Pt catalysed decomposition of H2O2 and it is understood that the Pt surface is highly susceptible to poisoning by sulphur-containing molecules. Here, we show that important extracellular thiols as well as basic organic molecules can significantly hamper the motion of catalytic microjet engines. This is due to two different mechanisms: (i) molecules such as dimethyl sulfoxide can quench the hydroxyl radicals produced at Pt surfaces and reduce the amount of oxygen gas generated and (ii) molecules containing -SH, -SSR, and -SCH3 moieties can poison the catalytically active platinum surface, inhibiting the motion of the jet engines. It is essential that the presence of such molecules in the environment be taken into consideration for future design and operation of catalytic microjet engines. We show this effect on catalytic micromotors prepared by both rolled-up and electrodeposition approaches, demonstrating that such poisoning is universal for Pt catalyzed micromotors. We believe that our findings will contribute significantly to this field to develop alternative systems or catalysts for self-propulsion when practical applications in the real environment are considered.

Preparation, characterization and catalytic application of CoFe2O4 nanoparticles in the synthesis of benzimidazoles

Science.gov (United States)

Borade, Ravikumar M.; Shinde, Pavan R.; Kale, Swati B.; Pawar, Rajendra P.

2018-05-01

A highly efficient magnetically recoverable cobalt ferrite nano-catalyst was prepared by sol-gel autocombustion method using glycine as green fuel. The prepared material has been characterized by X-ray powder diffraction and scanning. An investigation of its catalytic activity showed it to be a heterogeneous Lewis acid catalyst for the synthesis of substituted benzimidazoles. The aqueous ethanol used as green solvent for the reaction. The nm size range of these particles facilitates the catalysis process, as an increased surface area available for the reaction. The easy separation of the catalyst by an external magnet and their recovery and reuse in next cycle reaction are additional benefits.

Catalytic Fast Pyrolysis: A Review

Directory of Open Access Journals (Sweden)

Theodore Dickerson

2013-01-01

Full Text Available Catalytic pyrolysis is a promising thermochemical conversion route for lignocellulosic biomass that produces chemicals and fuels compatible with current, petrochemical infrastructure. Catalytic modifications to pyrolysis bio-oils are geared towards the elimination and substitution of oxygen and oxygen-containing functionalities in addition to increasing the hydrogen to carbon ratio of the final products. Recent progress has focused on both hydrodeoxygenation and hydrogenation of bio-oil using a variety of metal catalysts and the production of aromatics from bio-oil using cracking zeolites. Research is currently focused on developing multi-functional catalysts used in situ that benefit from the advantages of both hydrodeoxygenation and zeolite cracking. Development of robust, highly selective catalysts will help achieve the goal of producing drop-in fuels and petrochemical commodities from wood and other lignocellulosic biomass streams. The current paper will examine these developments by means of a review of existing literature.

Engineering design of a direct-cycle steam-generating blanket for a long-pulse fusion reactor

International Nuclear Information System (INIS)

Cort, G.E.; Hagenson, R.L.; Teasdale, R.W.; Fox, W.E.; Soran, P.D.; Cullingford, H.S.; Bathke, C.G.; Krakowski, R.A.

1979-01-01

A comprehensive neutronics, thermohydraulic, and mechanical design of a tritium-breeding blanket for use by a conceptual long-pulse Reversed-Field Pinch Reactor (RFPR) is described. On the basis of constraints imposed by cost and the desire to use existing technology, a direct-cycle steam system and stainless-steel construction were used. For reasons of plasma stability, the RFPR blanket supports a 20-mm-thick copper first wall. Located behind the 1.5-m-radius first wall is a 0.50-m-thick stainless-steel blanket containing a granular bed of Li 2 O through which flows low-pressure helium (0.1 MPa) for tritium extraction. Water/steam tubes radially penetrate this packed bed. The large thermal capacity and low thermal diffusivity of the Li 2 O blanket are sufficient to maintain a nearly constant temperature during the approx. 25-s burn period

Membrane Guanylate Cyclase catalytic Subdomain: Structure and Linkage with Calcium Sensors and Bicarbonate

Directory of Open Access Journals (Sweden)

Sarangan Ravichandran

2017-06-01

Full Text Available Membrane guanylate cyclase (MGC is a ubiquitous multi-switching cyclic GMP generating signaling machine linked with countless physiological processes. In mammals it is encoded by seven distinct homologous genes. It is a single transmembrane spanning multi-modular protein; composed of integrated blocks and existing in homo-dimeric form. Its core catalytic domain (CCD module is a common transduction center where all incoming signals are translated into the production of cyclic GMP, a cellular signal second messenger. Crystal structure of the MGC’s CCD does not exist and its precise identity is ill-defined. Here, we define it at a sub-molecular level for the phototransduction-linked MGC, the rod outer segment guanylate cyclase type 1, ROS-GC1. (1 The CCD is a conserved 145-residue structural unit, represented by the segment V820-P964. (2 It exists as a homo-dimer and contains seven conserved catalytic elements (CEs wedged into seven conserved motifs. (3 It also contains a conserved 21-residue neurocalcin δ-modulated structural domain, V836-L857. (4 Site-directed mutagenesis documents that each of the seven CEs governs the cyclase’s catalytic activity. (5 In contrast to the soluble and the bacterium MGC which use Mn2+-GTP substrate for catalysis, MGC CCD uses the natural Mg2+-GTP substrate. (6 Strikingly, the MGC CCD requires anchoring by the Transmembrane Domain (TMD to exhibit its major (∼92% catalytic activity; in isolated form the activity is only marginal. This feature is not linked with any unique sequence of the TMD; there is minimal conservation in TMD. Finally, (7 the seven CEs control each of four phototransduction pathways- -two Ca2+-sensor GCAPs-, one Ca2+-sensor, S100B-, and one bicarbonate-modulated. The findings disclose that the CCD of ROS-GC1 has built-in regulatory elements that control its signal translational activity. Due to conservation of these regulatory elements, it is proposed that these elements also control the

Direct comparison of enzyme histochemical and immunohistochemical methods to localize an enzyme

NARCIS (Netherlands)

van Noorden, Cornelis J. F.

2002-01-01

Immunohistochemical localization of enzymes is compared directly with localization of enzyme activity with (catalytic) enzyme histochemical methods. The two approaches demonstrate principally different aspects of an enzyme. The immunohistochemical method localizes the enzyme protein whether it is

Development of a coupled reactor with a catalytic combustor and steam reformer for a 5 kW solid oxide fuel cell system

International Nuclear Information System (INIS)

Kang, Sanggyu; Lee, Kanghun; Yu, Sangseok; Lee, Sang Min; Ahn, Kook-Young

2014-01-01

Highlights: • Proposes the scale-up strategy to develop a large-scale coupled reactor. • Investigation of performance of steam reformer coupled with catalytic combustor. • Experimental parameters are inlet temp., air excess ratio, SCR, fuel utilization. • Evaluation of the heat transfer distribution along the gas flow direction. • The mean value of methane conversion rate is approximately 93.4%. - Abstract: The methane (CH 4 ) conversion rate of a steam reformer can be increased by thermal integration with a catalytic combustor, called a coupled reactor. In the present study, a 5 kW coupled reactor has been developed based on a 1 kW coupled reactor in previous work. The geometric parameters of the space velocity, diameter and length of the coupled reactor selected from the 1 kW coupled reactor are tuned and applied to the design of the 5 kW coupled reactor. To confirm the scale-up strategy, the performance of 5 kW coupled reactor is experimentally investigated with variations of operating parameters such as the fuel utilization in the solid oxide fuel cell (SOFC) stack, the inlet temperature of the catalytic combustor, the excess air ratio of the catalytic combustor, and the steam to carbon ratio (SCR) in the steam reformer. The temperature distributions of coupled reactors are measured along the gas flow direction. The gas composition at the steam reformer outlet is measured to find the CH 4 conversion rate of the coupled reactor. The maximum value of the CH 4 conversion rate is approximately 93.4%, which means the proposed scale-up strategy can be utilized to develop a large-scale coupled reactor

Surface noble metal modified PdM/C (M = Ru, Pt, Au) as anode catalysts for direct ethanol fuel cells

International Nuclear Information System (INIS)

Mao, Han; Huang, Tao; Yu, Aishui

2016-01-01

In this article, we studied the surface noble metal modification on Pd nanoparticles, other than the homogeneous or core-shell structure. The surface modification will lead to the uneven constitution within the nanoparticles and thus more obvious optimization effect toward the catalyst brought by the lattice deformation. The surface of the as-prepared Pd nanoparticles was modified with Ru, Pt or Au by a moderate and green approach, respectively. XPS results confirm the interactive electron effects between Pd and the modified noble metal. Electrochemical measurements show that the surface noble metal modified catalysts not only show higher catalytic activity, but also better stability and durability. The PdM/C catalysts all exhibit good dispersion and very little agglomeration after long-term potential cycles toward ethanol oxidation. With only 10% metallic atomic ratio of Au, PdAu/C catalyst shows extraordinary catalytic activity and stability, the peak current reaches 1700 mA mg"−"1 Pd, about 2.5 times that of Pd/C. Moreover, the PdAu/C maintains 40% of the catalytic activity after 4500 potential cycles. - Highlights: • Pd-based catalysts with complicated exposed facets. • Much enhanced electrocatalytic activity and stability with about 10% noble metal M (M = Ru, Pt, Au) on Pd nanoparticles. • The outstanding electrocatalytic performance of PdAu/C towards ethanol oxidation after the Au modification.

Surface noble metal modified PdM/C (M = Ru, Pt, Au) as anode catalysts for direct ethanol fuel cells

Energy Technology Data Exchange (ETDEWEB)

Mao, Han; Huang, Tao, E-mail: huangt@fudan.edu.cn; Yu, Aishui, E-mail: asyu@fudan.edu.cn

2016-08-15

In this article, we studied the surface noble metal modification on Pd nanoparticles, other than the homogeneous or core-shell structure. The surface modification will lead to the uneven constitution within the nanoparticles and thus more obvious optimization effect toward the catalyst brought by the lattice deformation. The surface of the as-prepared Pd nanoparticles was modified with Ru, Pt or Au by a moderate and green approach, respectively. XPS results confirm the interactive electron effects between Pd and the modified noble metal. Electrochemical measurements show that the surface noble metal modified catalysts not only show higher catalytic activity, but also better stability and durability. The PdM/C catalysts all exhibit good dispersion and very little agglomeration after long-term potential cycles toward ethanol oxidation. With only 10% metallic atomic ratio of Au, PdAu/C catalyst shows extraordinary catalytic activity and stability, the peak current reaches 1700 mA mg{sup −1} Pd, about 2.5 times that of Pd/C. Moreover, the PdAu/C maintains 40% of the catalytic activity after 4500 potential cycles. - Highlights: • Pd-based catalysts with complicated exposed facets. • Much enhanced electrocatalytic activity and stability with about 10% noble metal M (M = Ru, Pt, Au) on Pd nanoparticles. • The outstanding electrocatalytic performance of PdAu/C towards ethanol oxidation after the Au modification.

Significance of the enzymatic properties of yeast S39A enolase to the catalytic mechanism.

Science.gov (United States)

Brewer, J M; Glover, C V; Holland, M J; Lebioda, L

1998-04-02

The S39A mutant of yeast enolase (isozyme 1), prepared by site-directed mutagenesis, has a relative Vmax of 0.01% and an activation constant for Mg2+ ca. 10-fold higher, compared with native enzyme. It is correctly folded. There is little effect of solvent viscosity on activity. We think that the loop Ser36-His43 fails to move to the 'closed' position upon catalytic Mg2+ binding, weakening several electrostatic interactions involved in the mechanism.

Oxyfuel combustion using a catalytic ceramic membrane reactor

Energy Technology Data Exchange (ETDEWEB)

Tan, Xiaoyao; Li, K. [Department of Chemical Engineering, Imperial College London, University of London, South Kensington, London SW7 2AZ (United Kingdom); Thursfield, A.; Metcalfe, I.S. [School of Chemical Engineering and Advanced Materials, Newcastle University, Newcastle upon Tyne, NE1 7RU (United Kingdom)

2008-02-29

Membrane catalytic combustion (MCC) is an environmentally friendly technique for heat and power generation from methane. This work demonstrates the performances of a MCC perovskite hollow fibre membrane reactor for the catalytic combustion of methane. The ionic-electronic La{sub 0.6}Sr{sub 0.4}Co{sub 0.2}Fe{sub 0.8}O{sub 3-{alpha}} (LSCF6428) mixed conductor, in the form of an oxygen-permeable hollow fibre membrane, has been prepared successfully by means of a phase-inversion spinning/sintering technique. For this process polyethersulfone (PESf) was used as a binder, N-methyl-2-pyrrollidone (NMP) as solvent and polyvinylpyrrolidone (PVP, K16-18) as an additive. With the prepared LSCF6428 hollow fibre membranes packed with catalyst, hollow fibre membrane reactors (HFMRs) have been assembled to perform the catalytic combustion of methane. A simple mathematical model that combines the local oxygen permeation rate with approximate catalytic reaction kinetics has been developed and can be used to predict the performance of the HFMRs for methane combustion. The effects of operating temperature and methane and air feed flow rates on the performance of the HFMR have been investigated both experimentally and theoretically. Both the methane conversion and oxygen permeation rate can be improved by means of coating platinum on the air side of the hollow fibre membranes. (author)

Fabrication of magnetically recyclable Fe3O4@Cu nanocomposites with high catalytic performance for the reduction of organic dyes and 4-nitrophenol

International Nuclear Information System (INIS)

Tang, Mingyi; Zhang, Sai; Li, Xianxian; Pang, Xiaobo; Qiu, Haixia

2014-01-01

A facile and efficient approach to synthesize Fe 3 O 4 @Cu nanocomposites using L-Lysine as a linker was developed. The morphology, composition and crystallinity of the Fe 3 O 4 @Cu nanocomposites were characterized by Fourier Transform infrared spectroscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, and powder X-ray diffraction. In addition, the magnetic properties were determined with vibrating sample magnetometer. The surface of the Fe 3 O 4 contained many small Cu nanoparticles with sizes of about 3 nm. It was found that the Fe 3 O 4 @Cu nanocomposites could catalyze the degradation of organic dyes. The catalytic activities of the Fe 3 O 4 @Cu nanocomposites for the reduction of nitrophenol were also studied. The Fe 3 O 4 @Cu nanocomposites are more efficient catalysts compared with Cu nanoparticles and can easily be recovered from the reaction mixture with magnet. The cost effective and recyclable Fe 3 O 4 @Cu nanocomposites provide an exciting new material for environmental protection applications. - Highlights: • Cu nanoparticles as small as 3 nm are synthesized. • Low cost Fe 3 O 4 @Cu magnetical nanoparticles show catalytic activity for organic dyes and 4-nitrophenol. • The Fe 3 O 4 @Cu display high catalytic activity after 13 cycles

COAL CONVERSION WASTEWATER TREATMENT BY CATALYTIC OXIDATION IN SUPERCRITICAL WATER; FINAL

International Nuclear Information System (INIS)

Phillip E. Savage

1999-01-01

Wastewaters from coal-conversion processes contain phenolic compounds in appreciable concentrations. These compounds need to be removed so that the water can be discharged or re-used. Catalytic oxidation in supercritical water is one potential means of treating coal-conversion wastewaters, and this project examined the reactions of phenol over different heterogeneous oxidation catalysts in supercritical water. More specifically, we examined the oxidation of phenol over a commercial catalyst and over bulk MnO(sub 2), bulk TiO(sub 2), and CuO supported on Al(sub 2) O(sub 3). We used phenol as the model pollutant because it is ubiquitous in coal-conversion wastewaters and there is a large database for non-catalytic supercritical water oxidation (SCWO) with which we can contrast results from catalytic SCWO. The overall objective of this research project is to obtain the reaction engineering information required to evaluate the utility of catalytic supercritical water oxidation for treating wastes arising from coal conversion processes. All four materials were active for catalytic supercritical water oxidation. Indeed, all four materials produced phenol conversions and CO(sub 2) yields in excess of those obtained from purely homogeneous, uncatalyzed oxidation reactions. The commercial catalyst was so active that we could not reliably measure reaction rates that were not limited by pore diffusion. Therefore, we performed experiments with bulk transition metal oxides. The bulk MnO(sub 2) and TiO(sub 2) catalysts enhance both the phenol disappearance and CO(sub 2) formation rates during SCWO. MnO(sub 2) does not affect the selectivity to CO(sub 2), or to the phenol dimers at a given phenol conversion. However, the selectivities to CO(sub 2) are increased and the selectivities to phenol dimers are decreased in the presence of TiO(sub 2) , which are desirable trends for a catalytic SCWO process. The role of the catalyst appears to be accelerating the rate of formation of

Efficient Catalytic Reduction of Hexavalent Chromium With Pd-decorated Carbon Nanotubes

Energy Technology Data Exchange (ETDEWEB)

Kim, Ji Dang; Choi, Hyun Chul [Chonnam National University, Gwangju (Korea, Republic of)

2016-05-15

Heavy metal pollution is currently a serious environmental issue. Chromium (Cr) and chromium compounds are commonly found in wastewater discharged by various industries such as wood preservation, leather tanning, electroplating, metal finishing, and the production of chemicals. Pd nanoparticles can easily be introduced into CNTs by performing DCC-activated amidation. Our TEM and XRD results indicate that well-dispersed metallic Pd nanoparticles are anchored on the surface of the amidated CNTs. The XPS results suggest that the Pd content of the sample is approximately 9.8 atomic %. In comparison with the commercial Pd catalyst, the prepared Pd-CNTs were demonstrated to exhibit good catalytic activity in the reduction of 4-NP by NaBH4. Moreover, the Pd-CNT catalyst can easily be separated by performing a simple filtration and reused over at least 10 cycles. This Pd-CNT catalyst is therefore believed to have significant potential for use as a reusable catalyst in the reduction of Cr(Vi)

Catalytic destruction of tar in biomass derived producer gas

International Nuclear Information System (INIS)

Zhang Ruiqin; Brown, Robert C.; Suby, Andrew; Cummer, Keith

2004-01-01

The purpose of this study is to investigate catalytic destruction of tar formed during gasification of biomass, with the goal of improving the quality of the producer gas. This work focuses on nickel based catalysts treated with alkali in an effort to promote steam gasification of the coke that deposits on catalyst surfaces. A tar conversion system consisting of a guard bed and catalytic reactor was designed to treat the producer gas from an air blown, fluidized bed biomass gasifier. The guard bed used dolomite to crack the heavy tars. The catalytic reactor was used to evaluate three commercial steam reforming catalysts. These were the ICI46-1 catalyst from Imperial Chemical Industry and Z409 and RZ409 catalysts from Qilu Petrochemical Corp. in China. A 0.5-3 l/min slipstream from a 5 tpd biomass gasifier was used to test the tar conversion system. Gas and tar were sampled before and after the tar conversion system to evaluate the effectiveness of the system. Changes in gas composition as functions of catalytic bed temperature, space velocity and steam/TOC (total organic carbon) ratio are presented. Structural changes in the catalysts during the tests are also described

The oceanic cycle and global atmospheric budget of carbonyl sulfide

Energy Technology Data Exchange (ETDEWEB)

Weiss, P.S.

1994-12-31

A significant portion of stratospheric air chemistry is influenced by the existence of carbonyl sulfide (COS). This ubiquitous sulfur gas represents a major source of sulfur to the stratosphere where it is converted to sulfuric acid aerosol particles. Stratospheric aerosols are climatically important because they scatter incoming solar radiation back to space and are able to increase the catalytic destruction of ozone through gas phase reactions on particle surfaces. COS is primarily formed at the surface of the earth, in both marine and terrestrial environments, and is strongly linked to natural biological processes. However, many gaps in the understanding of the global COS cycle still exist, which has led to a global atmospheric budget that is out of balance by a factor of two or more, and a lack of understanding of how human activity has affected the cycling of this gas. The goal of this study was to focus on COS in the marine environment by investigating production/destruction mechanisms and recalculating the ocean-atmosphere flux.

Enhanced catalytic hydrogenation activity of Ni/reduced graphene oxide nanocomposite prepared by a solid-state method

Science.gov (United States)

Li, Yizhao; Cao, Yali; Jia, Dianzeng

2018-01-01

A simple solid-state method has been applied to synthesize Ni/reduced graphene oxide (Ni/rGO) nanocomposite under ambient condition. Ni nanoparticles with size of 10-30 nm supported on reduced graphene oxide (rGO) nanosheets are obtained through one-pot solid-state co-reduction among nickel chloride, graphene oxide, and sodium borohydride. The Ni/rGO nanohybrid shows enhanced catalytic activity toward the reduction of p-nitrophenol (PNP) into p-aminophenol compared with Ni nanoparticles. The results of kinetic research display that the pseudo-first-order rate constant for hydrogenation reaction of PNP with Ni/rGO nanocomposite is 7.66 × 10-3 s-1, which is higher than that of Ni nanoparticles (4.48 × 10-3 s-1). It also presents superior turnover frequency (TOF, 5.36 h-1) and lower activation energy ( E a, 29.65 kJ mol-1) in the hydrogenation of PNP with Ni/rGO nanocomposite. Furthermore, composite catalyst can be magnetically separated and reused for five cycles. The large surface area and high electron transfer property of rGO support are beneficial for good catalytic performance of Ni/rGO nanocomposite. Our study demonstrates a simple approach to fabricate metal-rGO heterogeneous nanostructures with advanced functions.

PINGU: PredIction of eNzyme catalytic residues usinG seqUence information.

Directory of Open Access Journals (Sweden)

Priyadarshini P Pai

Full Text Available Identification of catalytic residues can help unveil interesting attributes of enzyme function for various therapeutic and industrial applications. Based on their biochemical roles, the number of catalytic residues and sequence lengths of enzymes vary. This article describes a prediction approach (PINGU for such a scenario. It uses models trained using physicochemical properties and evolutionary information of 650 non-redundant enzymes (2136 catalytic residues in a support vector machines architecture. Independent testing on 200 non-redundant enzymes (683 catalytic residues in predefined prediction settings, i.e., with non-catalytic per catalytic residue ranging from 1 to 30, suggested that the prediction approach was highly sensitive and specific, i.e., 80% or above, over the incremental challenges. To learn more about the discriminatory power of PINGU in real scenarios, where the prediction challenge is variable and susceptible to high false positives, the best model from independent testing was used on 60 diverse enzymes. Results suggested that PINGU was able to identify most catalytic residues and non-catalytic residues properly with 80% or above accuracy, sensitivity and specificity. The effect of false positives on precision was addressed in this study by application of predicted ligand-binding residue information as a post-processing filter. An overall improvement of 20% in F-measure and 0.138 in Correlation Coefficient with 16% enhanced precision could be achieved. On account of its encouraging performance, PINGU is hoped to have eventual applications in boosting enzyme engineering and novel drug discovery.

The effect of antimony-tin and indium-tin oxide supports on the catalytic activity of Pt nanoparticles for ammonia electro-oxidation

Energy Technology Data Exchange (ETDEWEB)

Silva, Júlio César M. [Department of Chemical & Biological Engineering, Centre for Catalysis Research and Innovation (CCRI), University of Ottawa, 161 Louis-Pasteur, Ottawa, ON K1N 6N5 (Canada); Instituto de Pesquisas Energéticas e Nucleares, IPEN/CNEN-SP, Av. Prof. Lineu Prestes, 2242 Cidade Universitária, CEP 05508-900, São Paulo, SP (Brazil); Piasentin, Ricardo M.; Spinacé, Estevam V.; Neto, Almir O. [Instituto de Pesquisas Energéticas e Nucleares, IPEN/CNEN-SP, Av. Prof. Lineu Prestes, 2242 Cidade Universitária, CEP 05508-900, São Paulo, SP (Brazil); Baranova, Elena A., E-mail: elena.baranova@uottawa.ca [Department of Chemical & Biological Engineering, Centre for Catalysis Research and Innovation (CCRI), University of Ottawa, 161 Louis-Pasteur, Ottawa, ON K1N 6N5 (Canada)

2016-09-01

Platinum nanoparticles supported on carbon (Pt/C) and carbon with addition of ITO (Pt/C-ITO (In{sub 2}O{sub 3}){sub 9}·(SnO{sub 2}){sub 1}) and ATO (Pt/C-ATO (SnO{sub 2}){sub 9}·(Sb{sub 2}O{sub 5}){sub 1}) oxides were prepared by sodium borohydride reduction method and used for ammonia electro-oxidation reaction (AmER) in alkaline media. The effect of the supports on the catalytic activity of Pt for AmER was investigated using electrochemical (cyclic voltammetry and chronoamperometry) and direct ammonia fuel cell (DAFC) experiments. X-ray diffraction (XRD) showed Pt peaks attributed to the face-centered cubic (fcc) structure, as well as peaks characteristic of In{sub 2}O{sub 3} in ITO support and cassiterite SnO{sub 2} phase of ATO support. According to transmission electron micrographs the mean particles sizes of Pt over carbon were 5.4, 4.9 and 4.7 nm for Pt/C, Pt/C-ATO and Pt/C-ITO, respectively. Pt/C-ITO catalysts showed the highest catalytic activity for ammonia electrooxidation in both electrochemical and fuel cell experiments. We attributed this to the presence of In{sub 2}O{sub 3} phase in ITO, which provides oxygenated or hydroxide species at lower potentials resulting in the removal of poisonous intermediate, i.e., atomic nitrogen (N{sub ads}) and promotion of ammonia electro-oxidation. - Highlights: • Oxide support effect on the catalytic activity of Pt towards ammonia electro-oxidation. • Direct ammonia fuel cell (DAFC) performance using Pt over different supports as anode. • Pt/C-ITO shows better catalytic activity for ammonia oxidation than Pt/C and Pt/C-ATO.

Triose phosphate isomerase deficiency is caused by altered dimerization--not catalytic inactivity--of the mutant enzymes.

Directory of Open Access Journals (Sweden)

Markus Ralser

Full Text Available Triosephosphate isomerase (TPI deficiency is an autosomal recessive disorder caused by various mutations in the gene encoding the key glycolytic enzyme TPI. A drastic decrease in TPI activity and an increased level of its substrate, dihydroxyacetone phosphate, have been measured in unpurified cell extracts of affected individuals. These observations allowed concluding that the different mutations in the TPI alleles result in catalytically inactive enzymes. However, despite a high occurrence of TPI null alleles within several human populations, the frequency of this disorder is exceptionally rare. In order to address this apparent discrepancy, we generated a yeast model allowing us to perform comparative in vivo analyses of the enzymatic and functional properties of the different enzyme variants. We discovered that the majority of these variants exhibit no reduced catalytic activity per se. Instead, we observed, the dimerization behavior of TPI is influenced by the particular mutations investigated, and by the use of a potential alternative translation initiation site in the TPI gene. Additionally, we demonstrated that the overexpression of the most frequent TPI variant, Glu104Asp, which displays altered dimerization features, results in diminished endogenous TPI levels in mammalian cells. Thus, our results reveal that enzyme deregulation attributable to aberrant dimerization of TPI, rather than direct catalytic inactivation of the enzyme, underlies the pathogenesis of TPI deficiency. Finally, we discovered that yeast cells expressing a TPI variant exhibiting reduced catalytic activity are more resistant against oxidative stress caused by the thiol-oxidizing reagent diamide. This observed advantage might serve to explain the high allelic frequency of TPI null alleles detected among human populations.

Catalytic zinc site and mechanism of the metalloenzyme PR-AMP cyclohydrolase.

Science.gov (United States)

D'Ordine, Robert L; Linger, Rebecca S; Thai, Carolyn J; Davisson, V Jo

2012-07-24

The enzyme N(1)-(5'-phosphoribosyl) adenosine-5'-monophosphate cyclohydrolase (PR-AMP cyclohydrolase) is a Zn(2+) metalloprotein encoded by the hisI gene. It catalyzes the third step of histidine biosynthesis, an uncommon ring-opening of a purine heterocycle for use in primary metabolism. A three-dimensional structure of the enzyme from Methanobacterium thermoautotrophicum has revealed that three conserved cysteine residues occur at the dimer interface and likely form the catalytic site. To investigate the functions of these cysteines in the enzyme from Methanococcus vannielii, a series of biochemical studies were pursued to test the basic hypothesis regarding their roles in catalysis. Inactivation of the enzyme activity by methyl methane thiosulfonate (MMTS) or 5,5'-dithiobis(2-nitrobenzoic acid) (DTNB) also compromised the Zn(2+) binding properties of the protein inducing loss of up to 90% of the metal. Overall reaction stoichiometry and the potassium cyanide (KCN) induced cleavage of the protein suggested that all three cysteines were modified in the process. The enzyme was protected from DTNB-induced inactivation by inclusion of the substrate N(1)-(5'-phosphoribosyl)adenosine 5'-monophosphate; (PR-AMP), while Mg(2+), a metal required for catalytic activity, enhanced the rate of inactivation. Site-directed mutations of the conserved C93, C109, C116 and the double mutant C109/C116 were prepared and analyzed for catalytic activity, Zn(2+) content, and reactivity with DTNB. Substitution of alanine for each of the conserved cysteines showed no measurable catalytic activity, and only the C116A was still capable of binding Zn(2+). Reactions of DTNB with the C109A/C116A double mutant showed that C93 is completely modified within 0.5 s. A model consistent with these data involves a DTNB-induced mixed disulfide linkage between C93 and C109 or C116, followed by ejection of the active site Zn(2+) and provides further evidence that the Zn(2+) coordination site involves the

Molecular dynamics characterization of five pathogenic factor X mutants associated with decreased catalytic activity

KAUST Repository

Abdel-Azeim, Safwat; Oliva, Romina M.; Chermak, Edrisse; De Cristofaro, Raimondo; Cavallo, Luigi

2014-01-01

Factor X (FX) is one of the major players in the blood coagulation cascade. Upon activation to FXa, it converts prothrombin to thrombin, which in turn converts fibrinogen into fibrin (blood clots). FXa deficiency causes hemostasis defects, such as intracranial bleeding, hemathrosis, and gastrointestinal blood loss. Herein, we have analyzed a pool of pathogenic mutations, located in the FXa catalytic domain and directly associated with defects in enzyme catalytic activity. Using chymotrypsinogen numbering, they correspond to D102N, T135M, V160A, G184S, and G197D. Molecular dynamics simulations were performed for 1.68 μs on the wild-type and mutated forms of FXa. Overall, our analysis shows that four of the five mutants considered, D102N, T135M, V160A, and G184S, have rigidities higher than those of the wild type, in terms of both overall protein motion and, specifically, subpocket S4 flexibility, while S1 is rather insensitive to the mutation. This acquired rigidity can clearly impact the substrate recognition of the mutants.

Molecular dynamics characterization of five pathogenic factor X mutants associated with decreased catalytic activity

KAUST Repository

Abdel-Azeim, Safwat

2014-11-11

Factor X (FX) is one of the major players in the blood coagulation cascade. Upon activation to FXa, it converts prothrombin to thrombin, which in turn converts fibrinogen into fibrin (blood clots). FXa deficiency causes hemostasis defects, such as intracranial bleeding, hemathrosis, and gastrointestinal blood loss. Herein, we have analyzed a pool of pathogenic mutations, located in the FXa catalytic domain and directly associated with defects in enzyme catalytic activity. Using chymotrypsinogen numbering, they correspond to D102N, T135M, V160A, G184S, and G197D. Molecular dynamics simulations were performed for 1.68 μs on the wild-type and mutated forms of FXa. Overall, our analysis shows that four of the five mutants considered, D102N, T135M, V160A, and G184S, have rigidities higher than those of the wild type, in terms of both overall protein motion and, specifically, subpocket S4 flexibility, while S1 is rather insensitive to the mutation. This acquired rigidity can clearly impact the substrate recognition of the mutants.

Antibody proteases: induction of catalytic response.

Science.gov (United States)

Gabibov, A G; Friboulet, A; Thomas, D; Demin, A V; Ponomarenko, N A; Vorobiev, I I; Pillet, D; Paon, M; Alexandrova, E S; Telegin, G B; Reshetnyak, A V; Grigorieva, O V; Gnuchev, N V; Malishkin, K A; Genkin, D D

2002-10-01

Most of the data accumulated throughout the years on investigation of catalytic antibodies indicate that their production increases on the background of autoimmune abnormalities. The different approaches to induction of catalytic response toward recombinant gp120 HIV-1 surface protein in mice with various autoimmune pathologies are described. The peptidylphosphonate conjugate containing structural part of gp120 molecule is used for reactive immunization of NZB/NZW F1, MRL, and SJL mice. The specific modification of heavy and light chains of mouse autoantibodies with Val-Ala-Glu-Glu-Glu-Val-PO(OPh)2 reactive peptide was demonstrated. Increased proteolytic activity of polyclonal antibodies in SJL mice encouraged us to investigate the production of antigen-specific catalytic antibodies on the background of induced experimental autoimmune encephalomyelitis (EAE). The immunization of autoimmune-prone mice with the engineered fusions containing the fragments of gp120 and encephalitogenic epitope of myelin basic protein (MBP(89-104)) was made. The proteolytic activity of polyclonal antibodies isolated from the sera of autoimmune mice immunized by the described antigen was shown. Specific immune response of SJL mice to these antigens was characterized. Polyclonal antibodies purified from sera of the immunized animals revealed proteolytic activity. The antiidiotypic approach to raise the specific proteolytic antibody as an "internal image" of protease is described. The "second order" monoclonal antibodies toward subtilisin Carlsberg revealed pronounced proteolytic activity.

Cytotoxicity from coupled redox cycling of autoxidizing xenobiotics and metals: a selective critical review and commentary on work-in-progress

Energy Technology Data Exchange (ETDEWEB)