Chemical kinetics: on the heterogeneous catalysis processes leading to an exchange between two phases. Example: isotopic exchange reactions; Cinetique chimique: sur les processus de catalyse 'heterogene' conduisant a un echange entre deux phases. Exemple: reactions d'echange isotopique

Energy Technology Data Exchange (ETDEWEB)

Dirian, G; Grandcollot, P [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1961-07-01

For an exchange reaction between a gaseous and a liquid phase proceeding by 'heterogeneous' catalysis in the liquid phase, diffusion in the liquid and the chemical reaction are two simultaneous and indivisible processes. We have nevertheless been able to establish criteria making it possible to distinguish between a really homogeneous kinetic process and a pseudo-homogeneous one. (author) [French] Pour une reaction d'echange entre une phase gazeuse et une phase liquide procedant par catalyse 'heterogene' en phase liquide, la diffusion dans le liquide et la reaction chimique sont deux etapes simultanees et indissociables. Nous avons pu neanmoins etablir des criteres permettant de distinguer entre une cinetique homogene vraie et une cinetique pseudo-homogene. (auteur)

Solution XAS Analysis for Exploring the Active Species in Homogeneous Vanadium Complex Catalysis

Science.gov (United States)

Nomura, Kotohiro; Mitsudome, Takato; Tsutsumi, Ken; Yamazoe, Seiji

2018-06-01

Selected examples in V K-edge X-ray Absorption Near Edge Structure (XANES) analysis of a series of vanadium complexes containing imido ligands (possessing metal-nitrogen double bond) in toluene solution have been introduced, and their pre-edge and the edge were affected by their structures and nature of ligands. Selected results in exploring the oxidation states of the active species in ethylene dimerization/polymerization using homogeneous vanadium catalysts [consisting of (imido)vanadium(V) complexes and Al cocatalysts] by X-ray absorption spectroscopy (XAS) analyses have been introduced. It has been demonstrated that the method should provide more clear information concerning the active species in situ, especially by combination with the other methods (NMR and ESR spectra, X-ray crystallographic analysis, and reaction chemistry), and should be powerful tool for study of catalysis mechanism as well as for the structural analysis in solution.

Catalysis in the Primordial World

Directory of Open Access Journals (Sweden)

Nenad Raos

2017-11-01

Full Text Available Catalysis provides orderly prebiotic synthesis and eventually its evolution into autocatalytic (self-reproduction systems. Research on homogeneous catalysis is concerned mostly with random peptide synthesis and the chances to produce catalytic peptide oligomers. Synthesis of ribose via formose reaction was found to be catalysed by B(OH4−, presumably released by weathering of borate minerals. Oxide and clay mineral surfaces provide catalytic sites for the synthesis of oligopeptides and oligonucleotides. Chemoautotrophic or iron-sulphur-world theory assumes that the first (pioneer organisms developed by catalytic processes on (Fe/NiS particles formed near/close hydrothermal vents. The review provides an overlay of possible catalytic reactions in prebiotic environment, discussing their selectivity (regioselectivity, stereoselectivity as well as geological availability of catalytic minerals and geochemical conditions enabling catalytic reactions on early Earth.

Tandem catalysis: a new approach to polymers.

Science.gov (United States)

Robert, Carine; Thomas, Christophe M

2013-12-21

The creation of polymers by tandem catalysis represents an exciting frontier in materials science. Tandem catalysis is one of the strategies used by Nature for building macromolecules. Living organisms generally synthesize macromolecules by in vivo enzyme-catalyzed chain growth polymerization reactions using activated monomers that have been formed within cells during complex metabolic processes. However, these biological processes rely on highly complex biocatalysts, thus limiting their industrial applications. In order to obtain polymers by tandem catalysis, homogeneous and enzyme catalysts have played a leading role in the last two decades. In the following feature article, we will describe selected published efforts to achieve these research goals.

Supported ionic liquids: versatile reaction and separation media

DEFF Research Database (Denmark)

Riisager, Anders; Fehrmann, Rasmus; Haumann, Marco

2006-01-01

The latest developments in supported ionic liquid phase (SILP) systems for catalysis and separation technology are surveyed. The SILP concept combines the advantages of homogeneous catalysis with heterogeneous process technology, and a variety of reactions have been studied where supported ionic ...... liquid catalysts proved to be more active and selective than common systems. In separation applications the use of supported ionic liquids can facilitate selective transport of substrates across membranes.......The latest developments in supported ionic liquid phase (SILP) systems for catalysis and separation technology are surveyed. The SILP concept combines the advantages of homogeneous catalysis with heterogeneous process technology, and a variety of reactions have been studied where supported ionic...

Catalysis seen in action

NARCIS (Netherlands)

Tromp, M.

2015-01-01

Synchrotron radiation techniques are widely applied in materials research and heterogeneous catalysis. In homogeneous catalysis, its use so far is rather limited despite its high potential. Here, insights in the strengths and limitations of X-ray spectroscopy technique in the field of homogeneous

Green chemistry by nano-catalysis

KAUST Repository

Polshettiwar, Vivek

2010-01-01

Nano-materials are important in many diverse areas, from basic research to various applications in electronics, biochemical sensors, catalysis and energy. They have emerged as sustainable alternatives to conventional materials, as robust high surface area heterogeneous catalysts and catalyst supports. The nano-sized particles increase the exposed surface area of the active component of the catalyst, thereby enhancing the contact between reactants and catalyst dramatically and mimicking the homogeneous catalysts. This review focuses on the use of nano-catalysis for green chemistry development including the strategy of using microwave heating with nano-catalysis in benign aqueous reaction media which offers an extraordinary synergistic effect with greater potential than these three components in isolation. To illustrate the proof-of-concept of this "green and sustainable" approach, representative examples are discussed in this article. © 2010 The Royal Society of Chemistry.

Conversion of CO2 via Visible Light Promoted Homogeneous Redox Catalysis

Directory of Open Access Journals (Sweden)

Bernhard Rieger

2012-11-01

Full Text Available This review gives an overview on the principles of light-promoted homogeneous redox catalysis in terms of applications in CO2 conversion. Various chromophores and the advantages of different structures and metal centers as well as optimization strategies are discussed. All aspects of the reduction catalyst site are restricted to CO2 conversion. An important focus of this review is the question of a replacement of the sacrificial donor which is found in most of the current publications. Furthermore, electronic parameters of supramolecular systems are reviewed with reference to the requisite of chromophores, oxidation and reduction sites.

Homogeneous Catalysis for Sustainable Hydrogen Storage in Formic Acid and Alcohols.

Science.gov (United States)

Sordakis, Katerina; Tang, Conghui; Vogt, Lydia K; Junge, Henrik; Dyson, Paul J; Beller, Matthias; Laurenczy, Gábor

2018-01-24

Hydrogen gas is a storable form of chemical energy that could complement intermittent renewable energy conversion. One of the main disadvantages of hydrogen gas arises from its low density, and therefore, efficient handling and storage methods are key factors that need to be addressed to realize a hydrogen-based economy. Storage systems based on liquids, in particular, formic acid and alcohols, are highly attractive hydrogen carriers as they can be made from CO 2 or other renewable materials, they can be used in stationary power storage units such as hydrogen filling stations, and they can be used directly as transportation fuels. However, to bring about a paradigm change in our energy infrastructure, efficient catalytic processes that release the hydrogen from these molecules, as well as catalysts that regenerate these molecules from CO 2 and hydrogen, are required. In this review, we describe the considerable progress that has been made in homogeneous catalysis for these critical reactions, namely, the hydrogenation of CO 2 to formic acid and methanol and the reverse dehydrogenation reactions. The dehydrogenation of higher alcohols available from renewable feedstocks is also described. Key structural features of the catalysts are analyzed, as is the role of additives, which are required in many systems. Particular attention is paid to advances in sustainable catalytic processes, especially to additive-free processes and catalysts based on Earth-abundant metal ions. Mechanistic information is also presented, and it is hoped that this review not only provides an account of the state of the art in the field but also offers insights into how superior catalytic systems can be obtained in the future.

Catalysis seen in action.

Science.gov (United States)

Tromp, Moniek

2015-03-06

Synchrotron radiation techniques are widely applied in materials research and heterogeneous catalysis. In homogeneous catalysis, its use so far is rather limited despite its high potential. Here, insights in the strengths and limitations of X-ray spectroscopy technique in the field of homogeneous catalysis are given, including new technique developments. A relevant homogeneous catalyst, used in the industrially important selective oligomerization of ethene, is taken as a worked-out example. Emphasis is placed on time-resolved operando X-ray absorption spectroscopy with outlooks to novel high energy resolution and emission techniques. All experiments described have been or can be done at the Diamond Light Source Ltd (Didcot, UK). © 2015 The Author(s) Published by the Royal Society. All rights reserved.

At the frontier between heterogeneous and homogeneous catalysis : hydrogenation of olefins and alkynes with soluble iron nanoparticles

NARCIS (Netherlands)

Rangheard, Claudine; Julián Fernández, César de; Phua, Pim-Huat; Hoorn, Johan; Lefort, Laurent; Vries, Johannes G. de

2010-01-01

The use of non-supported Fe nanoparticles in the hydrogenation of unsaturated C–C bonds is a green catalytic concept at the frontier between homogeneous and heterogeneous catalysis. Iron nanoparticles can be obtained by reducing Fe salts with strong reductants in various solvents. FeCl3 reduced by 3

Multicatalyst system in asymmetric catalysis

CERN Document Server

Zhou, Jian

2014-01-01

This book introduces multi-catalyst systems by describing their mechanism and advantages in asymmetric catalysis.  Helps organic chemists perform more efficient catalysis with step-by-step methods  Overviews new concepts and progress for greener and economic catalytic reactions  Covers topics of interest in asymmetric catalysis including bifunctional catalysis, cooperative catalysis, multimetallic catalysis, and novel tandem reactions   Has applications for pharmaceuticals, agrochemicals, materials, and flavour and fragrance

Pop-It Beads to Introduce Catalysis of Reaction Rate and Substrate Depletion Effects

Science.gov (United States)

Gehret, Austin U.

2017-01-01

A kinesthetic classroom activity was designed to help students understand enzyme activity and catalysis of reaction rate. Students served the role of enzymes by manipulating Pop-It Beads as the catalytic event. This activity illuminates the relationship between reaction rate and reaction progress by allowing students to experience first-hand the…

Practical Engineering Aspects of Catalysis in Microreactors

Czech Academy of Sciences Publication Activity Database

Křišťál, Jiří; Stavárek, Petr; Vajglová, Zuzana; Vondráčková, Magdalena; Pavlorková, Jana; Jiřičný, Vladimír

2015-01-01

Roč. 41, č. 12 (2015), s. 9357-9371 ISSN 0922-6168. [Pannonian Symposium on Catalysis /12./. Castle Trest, 16.09.2014-20.09.2014] Institutional support: RVO:67985858 Keywords : heterogeneous catalysis * homogeneous catalysis * photo catalysis Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 1.833, year: 2015

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

Science.gov (United States)

Ye, Rong

Catalysts, heterogeneous, homogeneous, and enzymatic, are comprised of nanometer-sized inorganic and/or organic components. They share molecular factors including charge, coordination, interatomic distance, bonding, and orientation of catalytically active atoms. By controlling the governing catalytic components and molecular factors, catalytic processes of a multichannel and multiproduct nature could be run in all three catalytic platforms to create unique end-products. Unifying the fields of catalysis is the key to achieving the goal of 100% selectivity in catalysis. Recyclable catalysts, especially those that display selective reactivity, are vital for the development of sustainable chemical processes. Among available catalyst platforms, heterogeneous catalysts are particularly well-disposed toward separation from the reaction mixture via filtration methods, which renders them readily recyclable. Furthermore, heterogeneous catalysts offer numerous handles - some without homogeneous analogues - for performance and selectivity optimization. These handles include nanoparticle size, pore profile of porous supports, surface ligands and interface with oxide supports, and flow rate through a solid catalyst bed. Despite these available handles, however, conventional heterogeneous catalysts are themselves often structurally heterogeneous compared to homogeneous catalysts, which complicates efforts to optimize and expand the scope of their reactivity and selectivity. Ongoing efforts are aimed to address the above challenge by heterogenizing homogeneous catalysts, which can be defined as the modification of homogeneous catalysts to render them in a separable (solid) phase from the starting materials and products. Specifically, we grow the small nanoclusters in dendrimers, a class of uniform polymers with the connectivity of fractal trees and generally radial symmetry. Thanks to their dense multivalency, shape persistence and structural uniformity, dendrimers have proven to

Controlled trifluoromethylation reactions of alkynes through visible-light photoredox catalysis.

Science.gov (United States)

Iqbal, Naeem; Jung, Jaehun; Park, Sehyun; Cho, Eun Jin

2014-01-07

The control of a reaction that can form multiple products is a highly attractive and challenging concept in synthetic chemistry. A set of valuable CF3 -containing molecules, namely trifluoromethylated alkenyl iodides, alkenes, and alkynes, were selectively generated from alkynes and CF3 I by environmentally benign and efficient visible-light photoredox catalysis. Subtle differences in the combination of catalyst, base, and solvent enabled the control of reactivity and selectivity for the reaction between an alkyne and CF3 I. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemical catalysis in biodiesel production (I): enzymatic catalysis processes

International Nuclear Information System (INIS)

Jachmarian, I.; Dobroyan, M.; Veira, J.; Vieitez, I.; Mottini, M.; Segura, N.; Grompone, M.

2009-01-01

There are some well known advantages related with the substitution of chemical catalysis by enzymatic catalysis processes.Some commercial immobilized lipases are useful for the catalysis of bio diesel reaction, which permits the achievement of high conversions and the recovery of high purity products, like a high quality glycerine. The main disadvantage of this alternative method is related with the last inactivation of the enzyme (by both the effect of the alcohol and the absorption of glycerol on catalyst surface), which added to the high cost of the catalyst, produces an unfavourable economical balance of the entire process. In the work the efficiency of two commercial immobilized lipases (Lipozyme TL IM y Novozyme 435 NNovozymes-Dinamarca) in the catalysis of the continuous transesterification of sunflower oil with different alcohols was studied. The intersolubility of the different mixturesinvolving reactans (S oil/alkyl esters/alcohol) and products (P mixtures with a higher content of 1% of glycerol,while for ethanol homogeneous mixtures were obtained at 12% of glycerol (44.44 12).Using and ethanolic substrate at the proportion S=19:75:6 and Lipozyme TL IM, it was possible to achieve a 98% of convertion to the corresponding biodiesel.When Novozymes 435 catalyzed the process it was possible to increase the oil concentration in the substrateaccording to proportion S=35:30:35, and a 78% conversion was obtained. The productivity shown by the firt enzyme was 70mg biodiesel g enzime-1, hora-1 while with the second one the productivity increased to 230. Results suggested that the convenient adjustement of substrate composition with the addition of biodiesel to reactants offers an efficient method for maximizing the enzyme productivity, hence improving the profitability of the enzymatic catalyzed process. (author)

Molecular water oxidation catalysis

CERN Document Server

Llobet, Antoni

2014-01-01

Photocatalytic water splitting is a promising strategy for capturing energy from the sun by coupling light harvesting and the oxidation of water, in order to create clean hydrogen fuel. Thus a deep knowledge of the water oxidation catalysis field is essential to be able to come up with useful energy conversion devices based on sunlight and water splitting. Molecular Water Oxidation Catalysis: A Key Topic for New Sustainable Energy Conversion Schemes presents a comprehensive and state-of-the-art overview of water oxidation catalysis in homogeneous phase, describing in detail the most importan

Numerical analysis for Darcy-Forchheimer flow in presence of homogeneous-heterogeneous reactions

Directory of Open Access Journals (Sweden)

Muhammad Ijaz Khan

Full Text Available A mathematical study is presented to investigate the influences of homogeneous and heterogeneous reactions in local similar flow caused by stretching sheet with a non-linear velocity and variable thickness. Porous medium effects are characterized by using Darcy-Forchheimer porous-media. A simple isothermal model of homogeneous-heterogeneous reactions is used. The multiphysical boundary value problem is dictated by ten thermophysical parameters: ratio of mass diffusion coefficients, Prandtl number, local inertia coefficient parameter, inverse Darcy number, shape parameter, surface thickness parameter, Hartman number, Homogeneous heat reaction, strength of homogeneous-heterogeneous reactions and Schmidt number. Resulting systems are computed by Runge-Kutta-Fehlberg method. Different shapes of velocity are noticed for n > 1 and n < 1. Keywords: Homogeneous-heterogeneous reactions, Non Darcy porous medium, Variable sheet thickness, Homogeneous heat reaction with stoichiometric coefficient, Runge-Kutta-Fehlberg method

Synchronicity of mononuclear and dinuclear events in homogeneous catalysis. Hydroformylation of cyclopentene using Rh4(CO)12 and HRe(CO)5 as precursors.

Science.gov (United States)

Li, Chuanzhao; Chen, Li; Garland, Marc

2007-10-31

The combined application of two or more metals in homogeneous catalysis can lead to synergistic effects; however, the phenomenological basis for these observations often goes undetermined. The hetero-bimetallic catalytic binuclear elimination reaction, a system involving both mononuclear and dinuclear intermediates, has been repeatedly suggested as a possible mechanism. In the present contribution, the simultaneous application of Rh4(CO)12 and HRe(CO)5 as precursors in the hydroformylation reaction leads to a very strong synergistic rate effect. In situ spectroscopic measurements confirm the presence of both mononuclear and dinuclear intermediates such as RCORh(CO)4 and RhRe(CO)9 in the active system. Moreover, kinetic analysis confirms interconversion of these intermediates as well as their statistical correlation with organic product formation. Specifically, the rate of hydrogen activation by RhRe(CO)9 is exactly equal to the rate of aldehyde formation from binuclear elimination between HRe(CO)5 and RCORh(CO)4 at all reaction conditions studied. Thus the catalytic events involving mononuclear species and those involving dinuclear species are synchronized. In the present experiments, the new topology is orders of magnitude more efficient than the corresponding unicyclic rhodium system.

Homogeneous-heterogeneous reactions in curved channel with porous medium

Science.gov (United States)

Hayat, T.; Ayub, Sadia; Alsaedi, A.

2018-06-01

Purpose of the present investigation is to examine the peristaltic flow through porous medium in a curved conduit. Problem is modeled for incompressible electrically conducting Ellis fluid. Influence of porous medium is tackled via modified Darcy's law. The considered model utilizes homogeneous-heterogeneous reactions with equal diffusivities for reactant and autocatalysis. Constitutive equations are formulated in the presence of viscous dissipation. Channel walls are compliant in nature. Governing equations are modeled and simplified under the assumptions of small Reynolds number and large wavelength. Graphical results for velocity, temperature, heat transfer coefficient and homogeneous-heterogeneous reaction parameters are examined for the emerging parameters entering into the problem. Results reveal an activation in both homogenous-heterogenous reaction effect and heat transfer rate with increasing curvature of the channel.

Constructing Bridges between Computational Tools in Heterogeneous and Homogeneous Catalysis

KAUST Repository

Falivene, Laura; Kozlov, Sergey M.; Cavallo, Luigi

2018-01-01

Better catalysts are needed to address numerous challenges faced by humanity. In this perspective, we review concepts and tools in theoretical and computational chemistry that can help to accelerate the rational design of homogeneous and heterogeneous catalysts. In particular, we focus on the following three topics: 1) identification of key intermediates and transition states in a reaction using the energetic span model, 2) disentanglement of factors influencing the relative stability of the key species using energy decomposition analysis and the activation strain model, and 3) discovery of new catalysts using volcano relationships. To facilitate wider use of these techniques across different areas, we illustrate their potentials and pitfalls when applied to the study of homogeneous and heterogeneous catalysts.

Constructing Bridges between Computational Tools in Heterogeneous and Homogeneous Catalysis

KAUST Repository

Falivene, Laura

2018-05-08

Better catalysts are needed to address numerous challenges faced by humanity. In this perspective, we review concepts and tools in theoretical and computational chemistry that can help to accelerate the rational design of homogeneous and heterogeneous catalysts. In particular, we focus on the following three topics: 1) identification of key intermediates and transition states in a reaction using the energetic span model, 2) disentanglement of factors influencing the relative stability of the key species using energy decomposition analysis and the activation strain model, and 3) discovery of new catalysts using volcano relationships. To facilitate wider use of these techniques across different areas, we illustrate their potentials and pitfalls when applied to the study of homogeneous and heterogeneous catalysts.

Surface and nanomolecular catalysis

CERN Document Server

Richards, Ryan

2006-01-01

Using new instrumentation and experimental techniques that allow scientists to observe chemical reactions and molecular properties at the nanoscale, the authors of Surface and Nanomolecular Catalysis reveal new insights into the surface chemistry of catalysts and the reaction mechanisms that actually occur at a molecular level during catalysis. While each chapter contains the necessary background and explanations to stand alone, the diverse collection of chapters shows how developments from various fields each contributed to our current understanding of nanomolecular catalysis as a whole. The

Catalysis of Supramolecular Hydrogelation

NARCIS (Netherlands)

Trausel, F.; Versluis, F.; Maity, C.; Poolman, J.M.; Lovrak, M.; van Esch, J.H.; Eelkema, R.

2016-01-01

ConspectusOne often thinks of catalysts as chemical tools to accelerate a reaction or to have a reaction run under more benign conditions. As such, catalysis has a role to play in the chemical industry and in lab scale synthesis that is not to be underestimated. Still, the role of catalysis in

CATALYSIS OF CHEMICAL PROCESSES: PARTICULAR ...

African Journals Online (AJOL)

IICBA01

secondary/high schools and universities, the inhibition of the chemical reactions is frequently ... As a result, the lesson catalysis is frequently included in chemistry education curricula at ... Misinterpretations in teaching and perception of catalysis ... profile is shown as a dependence of energy on reaction progress, without ...

Molecular catalysis science: Perspective on unifying the fields of catalysis.

Science.gov (United States)

Ye, Rong; Hurlburt, Tyler J; Sabyrov, Kairat; Alayoglu, Selim; Somorjai, Gabor A

2016-05-10

Colloidal chemistry is used to control the size, shape, morphology, and composition of metal nanoparticles. Model catalysts as such are applied to catalytic transformations in the three types of catalysts: heterogeneous, homogeneous, and enzymatic. Real-time dynamics of oxidation state, coordination, and bonding of nanoparticle catalysts are put under the microscope using surface techniques such as sum-frequency generation vibrational spectroscopy and ambient pressure X-ray photoelectron spectroscopy under catalytically relevant conditions. It was demonstrated that catalytic behavior and trends are strongly tied to oxidation state, the coordination number and crystallographic orientation of metal sites, and bonding and orientation of surface adsorbates. It was also found that catalytic performance can be tuned by carefully designing and fabricating catalysts from the bottom up. Homogeneous and heterogeneous catalysts, and likely enzymes, behave similarly at the molecular level. Unifying the fields of catalysis is the key to achieving the goal of 100% selectivity in catalysis.

Birnessite catalysis of the Maillard Reaction: Its significance in natural humification

Science.gov (United States)

Jokic, A.; Frenkel, A. I.; Vairavamurthy, M. A.; Huang, P. M.

Although mineral colloids are known to play a significant role in transforming organic matter in soils and sediments, there still are many gaps in our understanding of the mechanisms of organic-mineral interactions. In this study, we investigated the role of a major oxide-mineral birnessite (a form of Mn(IV) oxide) in catalyzing the condensation reaction between sugars and amino acids, the Maillard reaction, for forming humic substances. The Maillard reaction is perceived to be a major pathway in natural humification. Using a suite of spectroscopic methods (including ESR, XANES, EXAFS and 13C NMR), our results show that Mn(IV) oxide markedly accelerates the Maillard reaction between glucose and glycine at ranges of temperatures and pH typical of natural environments. These results demonstrate the importance of manganese oxide catalysis in the Maillard reaction, and its significance in the natural abiotic formation of humic substances.

Palladium-catalyzed coupling reactions

CERN Document Server

Molnár, Árpád

2013-01-01

This handbook and ready reference brings together all significant issues of practical importance for interested readers in one single volume. While covering homogeneous and heterogeneous catalysis, the text is unique in focusing on such important aspects as using different reaction media, microwave techniques or catalyst recycling. It also provides a comprehensive treatment of modern-day coupling reactions and emphasizes those topics that show potential for future development, such as continuous flow systems, water as a reaction medium, and catalyst immobilization, among others. With i

Metastable Structures in Cluster Catalysis from First-Principles: Structural Ensemble in Reaction Conditions and Metastability Triggered Reactivity.

Science.gov (United States)

Sun, Geng; Sautet, Philippe

2018-02-28

Reactivity studies on catalytic transition metal clusters are usually performed on a single global minimum structure. With the example of a Pt 13 cluster under a pressure of hydrogen, we show from first-principle calculations that low energy metastable structures of the cluster can play a major role for catalytic reactivity and that hence consideration of the global minimum structure alone can severely underestimate the activity. The catalyst is fluxional with an ensemble of metastable structures energetically accessible at reaction conditions. A modified genetic algorithm is proposed to comprehensively search for the low energy metastable ensemble (LEME) structures instead of merely the global minimum structure. In order to reduce the computational cost of density functional calculations, a high dimensional neural network potential is employed to accelerate the exploration. The presence and influence of LEME structures during catalysis is discussed by the example of H covered Pt 13 clusters for two reactions of major importance: hydrogen evolution reaction and methane activation. The results demonstrate that although the number of accessible metastable structures is reduced under reaction condition for Pt 13 clusters, these metastable structures can exhibit high activity and dominate the observed activity due to their unique electronic or structural properties. This underlines the necessity of thoroughly exploring the LEME structures in catalysis simulations. The approach enables one to systematically address the impact of isomers in catalysis studies, taking into account the high adsorbate coverage induced by reaction conditions.

Homogeneous deuteriodeiodination of iodinated tyrosine in angiotensin-I using synthesized triethyl[H-2]silane and Pd(0)

DEFF Research Database (Denmark)

Pedersen, Martin Holst Friborg; Martiny, Lars

2011-01-01

In our efforts to develop new reactions for the efficient labelling of peptides and proteins with tritium, we now report the use of silane hydrides together with homogenous Pd(0) catalysis for the protio- and deuteriodeiodination of an o-iodo-tyrosine containing peptide (angiotensin-I) performed...

Flows and chemical reactions in homogeneous mixtures

CERN Document Server

Prud'homme, Roger

2013-01-01

Flows with chemical reactions can occur in various fields such as combustion, process engineering, aeronautics, the atmospheric environment and aquatics. The examples of application chosen in this book mainly concern homogeneous reactive mixtures that can occur in propellers within the fields of process engineering and combustion: - propagation of sound and monodimensional flows in nozzles, which may include disequilibria of the internal modes of the energy of molecules; - ideal chemical reactors, stabilization of their steady operation points in the homogeneous case of a perfect mixture and c

Reciprocity theory of homogeneous reactions

Science.gov (United States)

Agbormbai, Adolf A.

1990-03-01

The reciprocity formalism is applied to the homogeneous gaseous reactions in which the structure of the participating molecules changes upon collision with one another, resulting in a change in the composition of the gas. The approach is applied to various classes of dissociation, recombination, rearrangement, ionizing, and photochemical reactions. It is shown that for the principle of reciprocity to be satisfied it is necessary that all chemical reactions exist in complementary pairs which consist of the forward and backward reactions. The backward reaction may be described by either the reverse or inverse process. The forward and backward processes must satisfy the same reciprocity equation. Because the number of dynamical variables is usually unbalanced on both sides of a chemical equation, it is necessary that this balance be established by including as many of the dynamical variables as needed before the reciprocity equation can be formulated. Statistical transformation models of the reactions are formulated. The models are classified under the titles free exchange, restricted exchange and simplified restricted exchange. The special equations for the forward and backward processes are obtained. The models are consistent with the H theorem and Le Chatelier's principle. The models are also formulated in the context of the direct simulation Monte Carlo method.

DNA-Accelerated Copper Catalysis of Friedel-Crafts Conjugate Addition/Enantioselective Protonation Reactions in Water

NARCIS (Netherlands)

García-Fernández, Almudena; Megens, Rik P.; Villarino, Lara; Roelfes, Gerard

2016-01-01

DNA-induced rate acceleration has been identified as one of the key elements for the success of the DNA-based catalysis concept. Here we report on a novel DNA-based catalytic Friedel-Crafts conjugate addition/enantioselective protonation reaction in water, which represents the first example of a

Complexes with charge transfer and ion-radical salts in catalysis

Energy Technology Data Exchange (ETDEWEB)

Krylov, O V [AN SSSR, Moscow. Inst. Khimicheskoj Fiziki

1978-01-01

Considered are the data experimentally proving formation of complexes with charge transfer as intermediate complexes in homogeneous and heterogeneous catalysis. Catalytic activity correlations with charge transfer energy (and in heterogeneous catalysis with width of semiconductor forbidden band can be useful while selection of catalysts (MoO/sub 3//MgO; V/sub 2/O/sub 5//MgO; MoO/sub 3//Al/sub 2/O/sub 3/; V/sub 2/O/sub 5//Al/sub 2/O/sub 3/). A review of papers on catalytic activity of the previously prepared complexes with charge transfer and ion-radical salts is given. The use of alkali metal complexes with aromatic compounds showed their high activity in hydrogenation reactions and proved principle possibility of activation of hydrogen and hydrocarbons by the systems which do not contain transfer metals.

: Recyclable, ligand free palladium(II) catalyst for Heck reaction

Indian Academy of Sciences (India)

well as heterogeneous palladium catalysts, generated from either palladium(0) compounds or palladium(II) acetate or chloride salts.6 Several ligands such as phosphines, phoshites, carbenes, thioethers have been successfully employed for this reaction.7 However, homogeneous catalysis results in problems of recovery.

Electrostatic catalysis of a Diels-Alder reaction

Science.gov (United States)

Aragonès, Albert C.; Haworth, Naomi L.; Darwish, Nadim; Ciampi, Simone; Bloomfield, Nathaniel J.; Wallace, Gordon G.; Diez-Perez, Ismael; Coote, Michelle L.

2016-03-01

It is often thought that the ability to control reaction rates with an applied electrical potential gradient is unique to redox systems. However, recent theoretical studies suggest that oriented electric fields could affect the outcomes of a range of chemical reactions, regardless of whether a redox system is involved. This possibility arises because many formally covalent species can be stabilized via minor charge-separated resonance contributors. When an applied electric field is aligned in such a way as to electrostatically stabilize one of these minor forms, the degree of resonance increases, resulting in the overall stabilization of the molecule or transition state. This means that it should be possible to manipulate the kinetics and thermodynamics of non-redox processes using an external electric field, as long as the orientation of the approaching reactants with respect to the field stimulus can be controlled. Here, we provide experimental evidence that the formation of carbon-carbon bonds is accelerated by an electric field. We have designed a surface model system to probe the Diels-Alder reaction, and coupled it with a scanning tunnelling microscopy break-junction approach. This technique, performed at the single-molecule level, is perfectly suited to deliver an electric-field stimulus across approaching reactants. We find a fivefold increase in the frequency of formation of single-molecule junctions, resulting from the reaction that occurs when the electric field is present and aligned so as to favour electron flow from the dienophile to the diene. Our results are qualitatively consistent with those predicted by quantum-chemical calculations in a theoretical model of this system, and herald a new approach to chemical catalysis.

Multi-catalysis cascade reactions based on the methoxycarbonylketene platform: diversity-oriented synthesis of functionalized non-symmetrical malonates for agrochemicals and pharmaceuticals.

Science.gov (United States)

Ramachary, Dhevalapally B; Venkaiah, Chintalapudi; Reddy, Y Vijayendar; Kishor, Mamillapalli

2009-05-21

In this paper we describe new multi-catalysis cascade (MCC) reactions for the one-pot synthesis of highly functionalized non-symmetrical malonates. These metal-free reactions are either five-step (olefination/hydrogenation/alkylation/ketenization/esterification) or six-step (olefination/hydrogenation/alkylation/ketenization/esterification/alkylation), and employ aldehydes/ketones, Meldrum's acid, 1,4-dihydropyridine/o-phenylenediamine, diazomethane, alcohols and active ethylene/acetylenes, and involve iminium-, self-, self-, self- and base-catalysis, respectively. Many of the products have direct application in agricultural and pharmaceutical chemistry.

Development of a reaction cell for in-situ/operando studies of surface of a catalyst under a reaction condition and during catalysis

Energy Technology Data Exchange (ETDEWEB)

Nguyen, Luan; Tao, Franklin, E-mail: franklin.tao.2011@gmail.com [Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556 (United States); Department of Chemical and Petroleum Engineering, University of Kansas, Lawrence, Kansas 66045 (United States)

2016-06-15

Tracking surface chemistry of a catalyst during catalysis is significant for fundamental understanding of catalytic performance of the catalyst since it allows for establishing an intrinsic correlation between surface chemistry of a catalyst at its working status and its corresponding catalytic performance. Ambient pressure X-ray photoelectron spectroscopy can be used for in-situ studies of surfaces of different materials or devices in a gas. To simulate the gaseous environment of a catalyst in a fixed-bed a flowing gaseous environment of reactants around the catalyst is necessary. Here, we report the development of a new flowing reaction cell for simulating in-situ study of a catalyst surface under a reaction condition in gas of one reactant or during catalysis in a mixture of reactants of a catalytic reaction. The homemade reaction cell is installed in a high vacuum (HV) or ultrahigh vacuum (UHV) environment of a chamber. The flowing gas in the reaction cell is separated from the HV or UHV environment through well sealings at three interfaces between the reaction cell and X-ray window, sample door and aperture of front cone of an energy analyzer. Catalyst in the cell is heated through infrared laser beam introduced through a fiber optics interfaced with the reaction cell through a homemade feedthrough. The highly localized heating on the sample holder and Au-passivated internal surface of the reaction cell effectively minimizes any unwanted reactions potentially catalyzed by the reaction cell. The incorporated laser heating allows a fast heating and a high thermal stability of the sample at a high temperature. With this cell, a catalyst at 800 °C in a flowing gas can be tracked readily.

Development of a reaction cell for in-situ/operando studies of surface of a catalyst under a reaction condition and during catalysis

International Nuclear Information System (INIS)

Nguyen, Luan; Tao, Franklin

2016-01-01

Tracking surface chemistry of a catalyst during catalysis is significant for fundamental understanding of catalytic performance of the catalyst since it allows for establishing an intrinsic correlation between surface chemistry of a catalyst at its working status and its corresponding catalytic performance. Ambient pressure X-ray photoelectron spectroscopy can be used for in-situ studies of surfaces of different materials or devices in a gas. To simulate the gaseous environment of a catalyst in a fixed-bed a flowing gaseous environment of reactants around the catalyst is necessary. Here, we report the development of a new flowing reaction cell for simulating in-situ study of a catalyst surface under a reaction condition in gas of one reactant or during catalysis in a mixture of reactants of a catalytic reaction. The homemade reaction cell is installed in a high vacuum (HV) or ultrahigh vacuum (UHV) environment of a chamber. The flowing gas in the reaction cell is separated from the HV or UHV environment through well sealings at three interfaces between the reaction cell and X-ray window, sample door and aperture of front cone of an energy analyzer. Catalyst in the cell is heated through infrared laser beam introduced through a fiber optics interfaced with the reaction cell through a homemade feedthrough. The highly localized heating on the sample holder and Au-passivated internal surface of the reaction cell effectively minimizes any unwanted reactions potentially catalyzed by the reaction cell. The incorporated laser heating allows a fast heating and a high thermal stability of the sample at a high temperature. With this cell, a catalyst at 800 °C in a flowing gas can be tracked readily.

Solid Base Catalysis

CERN Document Server

Ono, Yoshio

2011-01-01

The importance of solid base catalysts has come to be recognized for their environmentally benign qualities, and much significant progress has been made over the past two decades in catalytic materials and solid base-catalyzed reactions. The book is focused on the solid base. Because of the advantages over liquid bases, the use of solid base catalysts in organic synthesis is expanding. Solid bases are easier to dispose than liquid bases, separation and recovery of products, catalysts and solvents are less difficult, and they are non-corrosive. Furthermore, base-catalyzed reactions can be performed without using solvents and even in the gas phase, opening up more possibilities for discovering novel reaction systems. Using numerous examples, the present volume describes the remarkable role solid base catalysis can play, given the ever increasing worldwide importance of "green" chemistry. The reader will obtain an overall view of solid base catalysis and gain insight into the versatility of the reactions to whic...

µ-reactors for Heterogeneous Catalysis

DEFF Research Database (Denmark)

Jensen, Robert

is described in detail. Since heating and temperature measurement is an extremely important point in heterogeneous catalysis an entire chapter is dedicated to this subject. Three different types of heaters have been implemented and tested both for repeatability and homogeneity of the heating as well...

Catalysis Science Initiative: Catalyst Design by Discovery Informatics

Energy Technology Data Exchange (ETDEWEB)

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

2016-07-08

Catalysts selectively enhance the rates of chemical reactions toward desired products. Such reactions provide great benefit to society in major commercial sectors such as energy production, protecting the environment, and polymer products and thereby contribute heavily to the country’s gross national product. Our premise is that the level of fundamental understanding of catalytic events at the atomic and molecular scale has reached the point that more predictive methods can be developed to shorten the cycle time to new processes. The field of catalysis can be divided into two regimes: heterogeneous and homogeneous. For the heterogeneous catalysis regime, we have used the water-gas shift (WGS) reaction (CO + H2O + CO2 + H2O) over supported metals as a test bed. Detailed analysis and strong coupling of theory with experiment have led to the following conclusions: • The sequence of elementary steps goes through a COOH intermediate • The CO binding energy is a strong function of coverage of CO adsorbed on the surface in many systems • In the case of Au catalysts, the CO adsorption is generally too weak on surface with close atomic packing, but the enhanced binding at corner atoms (which are missing bonding partners) of cubo-octahedral nanoparticles increases the energy to a near optimal value and produces very active catalysts. • Reaction on the metal alone cannot account for the experimental results. The reaction is dual functional with water activation occurring at the metal-support interface. It is clear from our work that the theory component is essential, not only for prediction of new systems, but also for reconciling data and testing hypotheses regarding potential descriptors. Particularly important is the finding that the interface between nano-sized metal particles and the oxides that are used to support them represent a new state of matter in the sense that the interfacial bonding perturbs the chemical state of both metals atoms and the support

Reaction-transport simulations of non-oxidative methane conversion with continuous hydrogen removal: Homogeneous-heterogeneous methane reaction pathways

International Nuclear Information System (INIS)

Li, Lin; Borry, Richard W.; Iglesia, Enrique

2000-01-01

Detailed kinetic-transport models were used to explore thermodynamic and kinetic barriers in the non-oxidative conversion of CH4 via homogeneous and homogeneous-heterogeneous pathways and the effects of continuous hydrogen removal and of catalytic sites on attainable yields of useful C2-C10 products. The homogeneous kinetic model combines separately developed models for low-conversion pyrolysis and for chain growth to form large aromatics and carbon. The H2 formed in the reaction decreases CH4 pyrolysis rates and equilibrium conversions and it favors the formation of lighter products. The removal of H2 along tubular reactors with permeable walls increases reaction rates and equilibrium CH4 conversions. C2-C10 yields reach values greater than 90 percent at intermediate values of dimensionless transport rates (delta=1-10), defined as the ratio hydrogen transport and methane conversion rates. Homogeneous reactions require impractical residence times, even with H2 removal, because of slow initiation and chain transfer rates. The introduction of heterogeneous chain initiation pathways using surface sites that form methyl radicals eliminates the induction period without influencing the homogeneous product distribution. Methane conversion, however, occurs predominately in the chain transfer regime, within which individual transfer steps and the formation of C2 intermediates become limited by thermodynamic constraints. Catalytic sites alone cannot overcome these constraints. Catalytic membrane reactors with continuous H2 removal remove these thermodynamic obstacles and decrease the required residence time. Reaction rates become limited by homogeneous reactions of C2 products to form C6+ aromatics. Higher delta values lead to subsequent conversion of the desired C2-C10 products to larger polynuclear aromatics. We conclude that catalytic methane pyrolysis at the low temperatures required for restricted chain growth and the elimination of thermodynamics constraints via

Concepts in catalysis

International Nuclear Information System (INIS)

Boudart, M.

1992-01-01

This paper reports on concept in catalysis which are very important in heterogeneous catalysis, even today, when in spite of surface science, the complexity of events at a real catalytic surface is still evading the understanding necessary for design. In this paper the authors will attempt to give an update on evolving concepts in heterogeneous catalysis. The topics include: counting active centers on metal surfaces; the notion of turnover frequency for a catalytic cycle; the concept of structure (in) sensitive reactions; the ensemble (geometric) vs. The ligand (electronic) effect following Sachtler's school; the idea of a rate determining step and of a most abundant reactive intermediate; the effect of surface non-uniformity on catalytic kinetics; what makes catalytic cycles turnover

Next-Generation Catalysis for Renewables: Combining Enzymatic with Inorganic Heterogeneous Catalysis for Bulk Chemical Production

DEFF Research Database (Denmark)

Vennestrøm, Peter Nicolai Ravnborg; Christensen, C.H.; Pedersen, S.

2010-01-01

chemical platform under different conditions than those conventionally employed. Indeed, new process and catalyst concepts need to be established. Both enzymatic catalysis (biocatalysis) and heterogeneous inorganic catalysis are likely to play a major role and, potentially, be combined. One type...... of combination involves one-pot cascade catalysis with active sites from bio- and inorganic catalysts. In this article the emphasis is placed specifically on oxidase systems involving the coproduction of hydrogen peroxide, which can be used to create new in situ collaborative oxidation reactions for bulk...

Asymmetric C-C Bond-Formation Reaction with Pd: How to Favor Heterogeneous or Homogeneous Catalysis?

DEFF Research Database (Denmark)

Reimann, S.; Grunwaldt, Jan-Dierk; Mallat, T.

2010-01-01

The enantioselective allylic alkylation of (E)-1,3-diphenylallyl acetate was studied to clarify the heterogeneous or homogeneous character of the Pd/Al2O3-(R)-BINAP catalyst system. A combined approach was applied: the catalytic tests were completed with in situ XANES measurements to follow...

Competing role of catalysis-coagulation and catalysis-fragmentation in kinetic aggregation behaviours

International Nuclear Information System (INIS)

Li Xiao-Dong; Lin Zhen-Quan; Song Mei-Xia; Ke Jian-Hong

2010-01-01

We propose a kinetic aggregation model where species A aggregates evolve by the catalysis-coagulation and the catalysis-fragmentation, while the catalyst aggregates of the same species B or C perform self-coagulation processes. By means of the generalized Smoluchowski rate equation based on the mean-field assumption, we study the kinetic behaviours of the system with the catalysis-coagulation rate kernel K(i,j;l) ∝ l ν and the catalysis-fragmentation rate kernel F(i,j;l) ∝ l μ , where l is the size of the catalyst aggregate, and ν and μ are two parameters reflecting the dependence of the catalysis reaction on the size of the catalyst aggregate. The relation between the values of parameters ν and μ reflects the competing roles between the two catalysis processes in the kinetic evolution of species A. It is found that the competing roles of the catalysis-coagulation and catalysis-fragmentation in the kinetic aggregation behaviours are not determined simply by the relation between the two parameters ν and μ, but also depend on the values of these two parameters. When ν > μ and ν ≥ 0, the kinetic evolution of species A is dominated by the catalysis-coagulation and its aggregate size distribution a k (t) obeys the conventional or generalized scaling law; when ν k (t) approaches the scale-free form; and in other cases, a balance is established between the two competing processes at large times and a k (t) obeys a modified scaling law. (cross-disciplinary physics and related areas of science and technology)

A paradigm shift for radical SAM reactions: The organometallic intermediate Ω is central to catalysis.

Science.gov (United States)

Byer, Amanda S; Yang, Hao; McDaniel, Elizabeth C; Kathiresan, Venkatesan; Impano, Stella; Pagnier, Adrien; Watts, Hope; Denler, Carly; Vagstad, Anna; Piel, Jörn; Duschene, Kaitlin S; Shepard, Eric M; Shields, Thomas P; Scott, Lincoln G; Lilla, Edward A; Yokoyama, Kenichi; Broderick, William E; Hoffman, Brian M; Broderick, Joan B

2018-06-28

Radical S-adenosyl-L-methionine (SAM) en-zymes comprise a vast superfamily catalyzing diverse reactions essential to all life through ho-molytic SAM cleavage to liberate the highly-reactive 5-deoxyadenosyl radical (5-dAdo•). Our recent observation of a catalytically compe-tent organometallic intermediate Ω that forms dur-ing reaction of the radical SAM (RS) enzyme py-ruvate formate-lyase activating-enzyme (PFL-AE) was therefore quite surprising, and led to the question of its broad relevance in the superfamily. We now show that Ω in PFL-AE forms as an in-termediate under a variety of mixing order condi-tions, suggesting it is central to catalysis in this enzyme. We further demonstrate that Ω forms in a suite of RS enzymes chosen to span the totality of superfamily reaction types, implicating Ω as essential in catalysis across the RS superfamily. Finally, EPR and electron nuclear double reso-nance spectroscopy establish that Ω involves an Fe-C5 bond between 5-dAdo• and the [4Fe-4S] cluster. An analogous organometallic bond is found in the well-known adenosylcobalamin (co-enzyme B12) cofactor used to initiate radical reac-tions via a 5'-dAdo• intermediate. Generation of a 5'-dAdo• intermediate via homolytic metal-carbon bond cleavage thus appears to be similar for Ω and coenzyme B12. However coenzyme B12 is involved in enzymes catalyzing of only a small number (~12) of distinct reactions, while the RS superfamily has more than 100,000 distinct se-quences and over 80 reaction types character-ized to date. The appearance of Ω across the RS superfamily therefore dramatically enlarges the sphere of bio-organometallic chemistry in Nature.

New and future developments in catalysis catalysis by nanoparticles

CERN Document Server

Suib, Steven L

2013-01-01

New and Future Developments in Catalysis is a package of seven books that compile the latest ideas concerning alternate and renewable energy sources and the role that catalysis plays in converting new renewable feedstock into biofuels and biochemicals. Both homogeneous and heterogeneous catalysts and catalytic processes will be discussed in a unified and comprehensive approach. There will be extensive cross-referencing within all volumes. The use of catalysts in the nanoscale offers various advantages (increased efficiency and less byproducts), and these are discussed in this volume along with the various catalytic processes using nanoparticles. However, this is not without any risks and the safety aspects and effects on humans and the environment are still unknown. The present data as well as future needs are all part of this volume along with the economics involved. Offers in-depth coverage of all catalytic topics of current interest and outlines future challenges and research areas A clear and visual descr...

Cooperative catalysis designing efficient catalysts for synthesis

CERN Document Server

Peters, René

2015-01-01

Written by experts in the field, this is a much-needed overview of the rapidly emerging field of cooperative catalysis. The authors focus on the design and development of novel high-performance catalysts for applications in organic synthesis (particularly asymmetric synthesis), covering a broad range of topics, from the latest progress in Lewis acid / Br?nsted base catalysis to e.g. metal-assisted organocatalysis, cooperative metal/enzyme catalysis, and cooperative catalysis in polymerization reactions and on solid surfaces. The chapters are classified according to the type of cooperating acti

Cyclopalladated complexes in enantioselective catalysis

Energy Technology Data Exchange (ETDEWEB)

Dunina, Valeria V; Gorunova, Olga N; Zykov, P A; Kochetkov, Konstantin A

2011-01-31

The results of the use of optically active palladacycles in enantioselective catalysis of [3,3]-sigmatropic rearrangements, aldol condensation, the Michael reaction and cross-coupling are analyzed. Reactions with allylic substrates or reagents and some other transformations are considered.

Insights into reaction mechanisms in heterogeneous catalysis revealed by in situ NMR spectroscopy.

Science.gov (United States)

Blasco, Teresa

2010-12-01

This tutorial review intends to show the possibilities of in situ solid state NMR spectroscopy in the elucidation of reaction mechanisms and the nature of the active sites in heterogeneous catalysis. After a brief overview of the more usual experimental devices used for in situ solid state NMR spectroscopy measurements, some examples of applications taken from the recent literature will be presented. It will be shown that in situ NMR spectroscopy allows: (i) the identification of stable intermediates and transient species using indirect methods, (ii) to prove shape selectivity in zeolites, (iii) the study of reaction kinetics, and (iv) the determination of the nature and the role played by the active sites in a catalytic reaction. The approaches and methodology used to get this information will be illustrated here summarizing the most relevant contributions on the investigation of the mechanisms of a series of reactions of industrial interest: aromatization of alkanes on bifunctional catalysts, carbonylation reaction of methanol with carbon monoxide, ethylbenzene disproportionation, and the Beckmann rearrangement reaction. Special attention is paid to the research carried out on the role played by carbenium ions and alkoxy as intermediate species in the transformation of hydrocarbon molecules on solid acid catalysts.

Sustainable Catalysis_Energy efficient reactions and Applications

Science.gov (United States)

This book chapter discusses various catalysts for environmental remediation. Detailed information on catalysis using ferrate and ferrite oxidation, TiO2 photocatalysis, and new catalysts (i.e., graphene, perovskites and graphitic carbon nitride) is provided for the degradation of...

Arenethiolatecopper(I) complexes as homogeneous catalysts for Michael addition reactions

NARCIS (Netherlands)

Koten, G. van; Klaveren, M. van; Lambert, F.; Eijkelkamp, D.J.F.M.; Grove, D.M.

1994-01-01

Arenethiolatocopper(I) complexes are shown to be efficient homogeneous catalysts in Michael addition reactions of several Grignard reagents to acyclic enones; the addition products are formed with excellent chemoselectivity (>99%) and good enantioselectivity (76% e.e.).

Numerical simulation of catalysis combustion inside micro free-piston engine

International Nuclear Information System (INIS)

Wang, Qian; Zhang, Di; Bai, Jin; He, Zhixia

2016-01-01

Highlights: • A modeling study is applied on methane HCCI process of micro power device. • Mathematical formulas are established to predict the combustion characteristics. • Impacts of catalysis on the combustion characteristics are analyzed respectively. • The catalyst can improve the work steadily and reliability of micro power device. - Abstract: In order to investigate the catalytic combustion characteristics concerning homogeneous charge compression ignition (HCCI) in micro power device, numerical simulations with a 3D computation model that coupled motion of free piston and fluid dynamics of methane–air mixture flow were carried out and detailed gas-phase and surface catalytic reaction mechanisms of methane–air mixture were applied to the catalytic reactions model, a series of mathematical formula are established to predict the characteristics of compression ignition condition, impacts of catalysis on temperature, pressure, work capacity and other factors were analyzed respectively. Simulation results reveal that catalytic combustion facilitates the improvement of energy conversion efficiency and extends the ignition limit of methane–air mixture obviously, the ignition timing is brought forward as well, while compression ratio decreases and ignition delay period shrinks significantly. Numerical results demonstrate that the existence of catalytic wall helped to restrain the peak combustion pressure and maximum rate of pressure rise contributing to the steadily and reliability of operation inside micro free-piston power device.

An MM and QM Study of Biomimetic Catalysis of Diels-Alder Reactions Using Cyclodextrins

Directory of Open Access Journals (Sweden)

Wei Chen

2018-01-01

Full Text Available We performed a computational investigation of the mechanism by which cyclodextrins (CDs catalyze Diels-Alder reactions between 9-anthracenemethanol and N-cyclohexylmaleimide. Hydrogen bonds (Hbonds between N-cyclohexylmaleimide and the hydroxyl groups of cyclodextrins were suggested to play an important role in this catalytic process. However, our free energy calculations and molecular dynamics simulations showed that these Hbonds are not stable, and quantum mechanical calculations suggested that the reaction is not promoted by these Hbonds. The binding of 9-anthracenemethanol and N-cyclohexylmaleimide to cyclodextrins was the key to the catalytic process. Cyclodextrins act as a container to hold the two reactants in the cavity, pre-organize them for the reactions, and thus reduce the entropy penalty to the activation free energy. Dimethyl-β-CD was a better catalyst for this specific reaction than β-CD because of its stronger van der Waals interaction with the pre-organized reactants and its better performance in reducing the activation energy. This computational work sheds light on the mechanism of the catalytic reaction by cyclodextrins and introduces new perspectives of supramolecular catalysis.

Catalysis Research of Relevance to Carbon Management: Progress, Challenges, and Opportunities

Energy Technology Data Exchange (ETDEWEB)

Arakawa, Hironori; Aresta, Michele; Armor, John; Barteau, Mark; Beckman, Eric J.; Bell, Alexis T.; Bercaw, John E.; Creutz, Carol; Dinjus, Eckhard; Dixon, David A.; Domen, Kazunari; Dubois, Daniel L.; Eckert, Juergen; Fujita, Etsuko; Gibson, Dorothy H.; Goddard, William A.; Goodman, Wayne D.; Keller, Jay; Kubas, Gregory J.; Kung, Harold H.; Lyons, James E.; Manzer, Leo; Marks, Tobin J.; Morokuma, Keiji; Nicholas, Kenneth M.; Periana, Roy; Que, Lawrence; Rostrup-Nielson, Jens; Sachtler, Woflgang M H.; Schmidt, Lanny D.; Sen, Ayusman; Somorjai, Gabor A.; Stair, Peter C.; Stults, Bailey R.; Tumas, William

2001-04-11

The goal of the 'Opportunities for Catalysis Research in Carbon Management' workshop was to review within the context of greenhouse gas/carbon issues the current state of knowledge, barriers to further scientific and technological progress, and basic scientific research needs in the areas of H{sub 2} generation and utilization, light hydrocarbon activation and utilization, carbon dioxide activation, utilization, and sequestration, emerging techniques and research directions in relevant catalysis research, and in catalysis for more efficient transportation engines. Several overarching themes emerge from this review. First and foremost, there is a pressing need to better understand in detail the catalytic mechanisms involved in almost every process area mentioned above. This includes the structures, energetics, lifetimes, and reactivities of the species thought to be important in the key catalytic cycles. As much of this type of information as is possible to acquire would also greatly aid in better understanding perplexing, incomplete/inefficient catalytic cycles and in inventing new, efficient ones. The most productive way to attack such problems must include long-term, in-depth fundamental studies of both commercial and model processes, by conventional research techniques and, importantly, by applying various promising new physicochemical and computational approaches which would allow incisive, in situ elucidation of reaction pathways. There is also a consensus that more exploratory experiments, especially high-risk, unconventional catalytic and model studies, should be undertaken. Such an effort will likely require specialized equipment, instrumentation, and computational facilities. The most expeditious and cost-effective means to carry out this research would be by close coupling of academic, industrial, and national laboratory catalysis efforts worldwide. Completely new research approaches should be vigorously explored, ranging from novel compositions

At the frontier between heterogeneous and homogeneous catalysis: hydrogenation of olefins and alkynes with soluble iron nanoparticles.

Science.gov (United States)

Rangheard, Claudine; de Julián Fernández, César; Phua, Pim-Huat; Hoorn, Johan; Lefort, Laurent; de Vries, Johannes G

2010-09-28

The use of non-supported Fe nanoparticles in the hydrogenation of unsaturated C-C bonds is a green catalytic concept at the frontier between homogeneous and heterogeneous catalysis. Iron nanoparticles can be obtained by reducing Fe salts with strong reductants in various solvents. FeCl(3) reduced by 3 equivalents of EtMgCl forms an active catalyst for the hydrogenation of a range of olefins and alkynes. Olefin hydrogenation is relatively fast at 5 bar using 5 mol% of catalyst. The catalyst is also active for terminal olefins and 1,1' and 1,2-cis disubstituted olefins while trans-olefins react much slower. 1-Octyne is hydrogenated to mixtures of 1-octene and octane. Kinetic studies led us to propose a mechanism for this latter transformation where octane is obtained by two different pathways. Characterization of the nanoparticles via TEM, magnetic measurements and poisoning experiments were undertaken to understand the true nature of our catalyst.

New and future developments in catalysis catalysis for remediation and environmental concerns

CERN Document Server

Suib, Steven L

2013-01-01

New and Future Developments in Catalysis is a package of seven books that compile the latest ideas concerning alternate and renewable energy sources and the role that catalysis plays in converting new renewable feedstock into biofuels and biochemicals. Both homogeneous and heterogeneous catalysts and catalytic processes will be discussed in a unified and comprehensive approach. There will be extensive cross-referencing within all volumes. The various sources of environmental pollution are the theme of this volume. The volume lists all current environmentally friendly catalytic chemical processes used for environmental remediation and critically compares their economic viability. Offers in-depth coverage of all catalytic topics of current interest and outlines future challenges and research areas A clear and visual description of all parameters and conditions, enabling the reader to draw conclusions for a particular case Outlines the catalytic processes applicable to energy generation and design of green proce...

Immobilised Homogeneous Catalysts for Sequential Fine Chemical Synthesis : Functionalised Organometallics for Nanotechnology

NARCIS (Netherlands)

McDonald, A.R.

2008-01-01

The work described in this thesis has demonstrated the application of heterogenised homogeneous catalysts. We have shown that by coupling a homogeneous catalyst to a heterogeneous support we could combine the benefits of two major fields of catalysis: retain the high selectivity of homogeneous

Selective Homogeneous Catalysis in Asymmetric Synthesis

DEFF Research Database (Denmark)

Fristrup, Peter

of twelve “substrate-probes”, which were designed and synthesized specifically for this purpose. Both the stoichiometric reaction with OsO4 in toluene and the more environmentally benign catalytic reaction in a two-phase system were studied. The obtained experimental results were in good agreement...

Molecular catalysis and high-volume organic synthesis

Energy Technology Data Exchange (ETDEWEB)

Khidekel, M L; Vasserberg, V E

1977-01-01

The field of catalysis is very wide. The properties of catalysts are briefly reviewed and compared with the properties of enzymes. Various uses of enxymes in industry (sugar from corn, cellulose breakdown, etc.) are pointed out. The types of homogeneous and heterogeneous catalysts for use in organic synthesis are discussed. 48 refs. (SJR)

The Development of Visible-Light Photoredox Catalysis in Flow.

Science.gov (United States)

Garlets, Zachary J; Nguyen, John D; Stephenson, Corey R J

2014-04-01

Visible-light photoredox catalysis has recently emerged as a viable alternative for radical reactions otherwise carried out with tin and boron reagents. It has been recognized that by merging photoredox catalysis with flow chemistry, slow reaction times, lower yields, and safety concerns may be obviated. While flow reactors have been successfully applied to reactions carried out with UV light, only recent developments have demonstrated the same potential of flow reactors for the improvement of visible-light-mediated reactions. This review examines the initial and continuing development of visible-light-mediated photoredox flow chemistry by exemplifying the benefits of flow chemistry compared with conventional batch techniques.

Mitoxantrone removal by electrochemical method: A comparison of homogenous and heterogenous catalytic reactions

Directory of Open Access Journals (Sweden)

Abbas Jafarizad

2017-08-01

Full Text Available Background: Mitoxantrone (MXT is a drug for cancer therapy and a hazardous pharmaceutical to the environment which must be removed from contaminated waste streams. In this work, the removal of MXT by the electro-Fenton process over heterogeneous and homogenous catalysts is reported. Methods: The effects of the operational conditions (reaction medium pH, catalyst concentration and utilized current intensity were studied. The applied electrodes were carbon cloth (CC without any processing (homogenous process, graphene oxide (GO coated carbon cloth (GO/CC (homogenous process and Fe3O4@GO nanocomposite coated carbon cloth (Fe3O4@GO/CC (heterogeneous process. The characteristic properties of the electrodes were determined by atomic force microscopy (AFM, field emission scanning electron microscopy (FE-SEM and cathode polarization. MXT concentrations were determined by using ultraviolet-visible (UV-Vis spectrophotometer. Results: In a homogenous reaction, the high concentration of Fe catalyst (>0.2 mM decreased the MXT degradation rate. The results showed that the Fe3O4@GO/CC electrode included the most contact surface. The optimum operational conditions were pH 3.0 and current intensity of 450 mA which resulted in the highest removal efficiency (96.9% over Fe3O4@GO/CC electrode in the heterogeneous process compared with the other two electrodes in a homogenous process. The kinetics of the MXT degradation was obtained as a pseudo-first order reaction. Conclusion: The results confirmed the high potential of the developed method to purify contaminated wastewaters by MXT.

bond activation and catalysis by Ru -pac complexes

Indian Academy of Sciences (India)

and their reactivity towards oxidation of a few organic compounds. Keywords. Kinetics; catalysis; -O–O- bond activation; Ru-pac complex; oxidation. 1. Introduction. Ru-pac complexes exhibit catalytic properties,1 in homogeneous conditions in the presence of oxygen atom donors, that mimic the biological enzymatic oxi-.

Relation between Hydrogen Evolution and Hydrodesulfurization Catalysis

DEFF Research Database (Denmark)

Šaric, Manuel; Moses, Poul Georg; Rossmeisl, Jan

2016-01-01

A relation between hydrogen evolution and hydrodesulfurization catalysis was found by density functional theory calculations. The hydrogen evolution reaction and the hydrogenation reaction in hydrodesulfurization share hydrogen as a surface intermediate and, thus, have a common elementary step...

Pickering interfacial catalysis for biphasic systems: from emulsion design to green reactions.

Science.gov (United States)

Pera-Titus, Marc; Leclercq, Loïc; Clacens, Jean-Marc; De Campo, Floryan; Nardello-Rataj, Véronique

2015-02-09

Pickering emulsions are surfactant-free dispersions of two immiscible fluids that are kinetically stabilized by colloidal particles. For ecological reasons, these systems have undergone a resurgence of interest to mitigate the use of synthetic surfactants and solvents. Moreover, the use of colloidal particles as stabilizers provides emulsions with original properties compared to surfactant-stabilized emulsions, microemulsions, and micellar systems. Despite these specific advantages, the application of Pickering emulsions to catalysis has been rarely explored. This Minireview describes very recent examples of hybrid and composite amphiphilic materials for the design of interfacial catalysts in Pickering emulsions with special emphasis on their assets and challenges for industrially relevant biphasic reactions in fine chemistry, biofuel upgrading, and depollution. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Impact of Cattaneo-Christov Heat Flux in Jeffrey Fluid Flow with Homogeneous-Heterogeneous Reactions.

Directory of Open Access Journals (Sweden)

Tasawar Hayat

Full Text Available Two-dimensional stretched flow of Jeffrey fluid in view of Cattaneo-Christov heat flux is addressed. Effects of homogeneous-heterogeneous reactions are also considered. Suitable transformations are used to form ordinary differential equations. Convergent series solutions are computed. Impact of significant parameters on the velocity, temperature, concentration and skin friction coefficient is addressed. Analysis of thermal relaxation is made. The obtained results show that ratio of relaxation to retardation times and Deborah number have inverse relation for velocity profile. Temperature distribution has decreasing behavior for Prandtl number and thermal relaxation time. Also concentration decreases for larger values of strength of homogeneous reaction parameter while it increases for strength of heterogeneous reaction parameter.

Impact of Cattaneo-Christov Heat Flux in Jeffrey Fluid Flow with Homogeneous-Heterogeneous Reactions.

Science.gov (United States)

Hayat, Tasawar; Qayyum, Sumaira; Imtiaz, Maria; Alsaedi, Ahmed

2016-01-01

Two-dimensional stretched flow of Jeffrey fluid in view of Cattaneo-Christov heat flux is addressed. Effects of homogeneous-heterogeneous reactions are also considered. Suitable transformations are used to form ordinary differential equations. Convergent series solutions are computed. Impact of significant parameters on the velocity, temperature, concentration and skin friction coefficient is addressed. Analysis of thermal relaxation is made. The obtained results show that ratio of relaxation to retardation times and Deborah number have inverse relation for velocity profile. Temperature distribution has decreasing behavior for Prandtl number and thermal relaxation time. Also concentration decreases for larger values of strength of homogeneous reaction parameter while it increases for strength of heterogeneous reaction parameter.

New and future developments in catalysis activation of carbon dioxide

CERN Document Server

Suib, Steven L

2013-01-01

New and Future Developments in Catalysis is a package of books that compile the latest ideas concerning alternate and renewable energy sources and the role that catalysis plays in converting new renewable feedstock into biofuels and biochemicals. Both homogeneous and heterogeneous catalysts and catalytic processes will be discussed in a unified and comprehensive approach. There will be extensive cross-referencing within all volumes. This volume presents a complete picture of all carbon dioxide (CO2) sources, outlines the environmental concerns regarding CO2, and critica

Towards a methanol economy based on homogeneous catalysis: methanol to H2 and CO2 to methanol

DEFF Research Database (Denmark)

Alberico, E.; Nielsen, Martin

2015-01-01

The possibility to implement both the exhaustive dehydrogenation of aqueous methanol to hydrogen and CO2 and the reverse reaction, the hydrogenation of CO2 to methanol and water, may pave the way to a methanol based economy as part of a promising renewable energy system. Recently, homogeneous...

Mechanistic studies on the phosphoramidite coupling reaction in oligonucleotide synthesis. I. Evidence for nudeophilic catalysis by tetrazole and rate variations with the phosphorus substituents

DEFF Research Database (Denmark)

Dahl, Bjarne H.; Nielsen, John; Dahl, Otto

1987-01-01

, and that dialkylammonium tetrazolide salts are inhibitors. These and other facts are evidence that the reactions are subjected to nucleophilic catalysis by tetrazole, in addition to acid catalysis. The rate variations with phosphorus substituents of 1a-h are NEt 2 > NRr12 > N(CH 2CH 2)O > NMePh, and OMe > OCH 2CH 2CN......Tetrazole catalyzed reactions of a series of phosphoramidites, 5′ -O- DMTdT-3′-O-P(OR 1)NRNR22 (1a-h), with 3′ O-SiBu tPh 2-6-N-benzoyl-dA (2a) in acetonitrite solution have been studied. It is found that the coupling rate depends very much on whether tetrazole is added before or after 2a...

Seventh BES [Basic Energy Sciences] catalysis and surface chemistry research conference

International Nuclear Information System (INIS)

1990-03-01

Research programs on catalysis and surface chemistry are presented. A total of fifty-seven topics are included. Areas of research include heterogeneous catalysis; catalysis in hydrogenation, desulfurization, gasification, and redox reactions; studies of surface properties and surface active sites; catalyst supports; chemical activation, deactivation; selectivity, chemical preparation; molecular structure studies; sorption and dissociation. Individual projects are processed separately for the data bases

Seventh BES (Basic Energy Sciences) catalysis and surface chemistry research conference

Energy Technology Data Exchange (ETDEWEB)

1990-03-01

Research programs on catalysis and surface chemistry are presented. A total of fifty-seven topics are included. Areas of research include heterogeneous catalysis; catalysis in hydrogenation, desulfurization, gasification, and redox reactions; studies of surface properties and surface active sites; catalyst supports; chemical activation, deactivation; selectivity, chemical preparation; molecular structure studies; sorption and dissociation. Individual projects are processed separately for the data bases. (CBS)

One- and two-dimensional infrared spectroscopic studies of solution-phase homogeneous catalysis and spin-forbidden reactions

Energy Technology Data Exchange (ETDEWEB)

Sawyer, Karma Rae [Univ. of California, Berkeley, CA (United States)

2008-12-01

Understanding chemical reactions requires the knowledge of the elementary steps of breaking and making bonds, and often a variety of experimental techniques are needed to achieve this goal. The initial steps occur on the femto- through picosecond time-scales, requiring the use of ultrafast spectroscopic methods, while the rate-limiting steps often occur more slowly, requiring alternative techniques. Ultrafast one and two-dimensional infrared and step-scan FTIR spectroscopies are used to investigate the photochemical reactions of four organometallic complexes. The analysis leads to a detailed understanding of mechanisms that are general in nature and may be applicable to a variety of reactions.

Outcome of homogeneous and heterogeneous reactions in Darcy-Forchheimer flow with nonlinear thermal radiation and convective condition

Directory of Open Access Journals (Sweden)

T. Hayat

Full Text Available The present analysis aims to report the consequences of nonlinear radiation, convective condition and heterogeneous-homogeneous reactions in Darcy-Forchheimer flow over a non-linear stretching sheet with variable thickness. Non-uniform magnetic field and nonuniform heat generation/absorption are accounted. The governing boundary layer partial differential equations are converted into a system of nonlinear ordinary differential equations. The computations are organized and the effects of physical variables such as thickness parameter, power index, Hartman number, inertia and porous parameters, radiation parameter, Biot number, Prandtl number, ratio parameter, heat generation parameter and homogeneous-heterogeneous reaction parameter are investigated. The variations of skin friction coefficient and Nusselt number for different interesting variables are plotted and discussed. It is noticed that Biot number and heat generation variable lead to enhance the temperature distribution. The solutal boundary layer thickness decreases for larger homogeneous variable while reverse trend is seen for heterogeneous reaction. Keywords: Variable sheet thickness, Darcy-Forchheimer flow, Homogeneous-heterogeneous reactions, Power-law surface velocity, Convective condition, Heat generation/absorption, Nonlinear radiation

"Nanocrystal bilayer for tandem catalysis"

Energy Technology Data Exchange (ETDEWEB)

Yamada, Yusuke; Tsung, Chia Kuang; Huang, Wenyu; Huo, Ziyang; E.Habas, Susan E; Soejima, Tetsuro; Aliaga, Cesar E; Samorjai, Gabor A; Yang, Peidong

2011-01-24

Supported catalysts are widely used in industry and can be optimized by tuning the composition and interface of the metal nanoparticles and oxide supports. Rational design of metal-metal oxide interfaces in nanostructured catalysts is critical to achieve better reaction activities and selectivities. We introduce here a new class of nanocrystal tandem catalysts that have multiple metal-metal oxide interfaces for the catalysis of sequential reactions. We utilized a nanocrystal bilayer structure formed by assembling platinum and cerium oxide nanocube monolayers of less than 10 nm on a silica substrate. The two distinct metal-metal oxide interfaces, CeO2-Pt and Pt-SiO2, can be used to catalyse two distinct sequential reactions. The CeO2-Pt interface catalysed methanol decomposition to produce CO and H2, which were subsequently used for ethylene hydroformylation catalysed by the nearby Pt-SiO2 interface. Consequently, propanal was produced selectively from methanol and ethylene on the nanocrystal bilayer tandem catalyst. This new concept of nanocrystal tandem catalysis represents a powerful approach towards designing high-performance, multifunctional nanostructured catalysts

Electro-Catalysis System for Biodiesel Synthesis from Palm Oil over Dielectric-Barrier Discharge Plasma Reactor

Directory of Open Access Journals (Sweden)

Istadi Istadi

2014-07-01

Full Text Available Biodiesel synthesis reaction routes from palm oil using plasma electro-catalysis process over Dielectric-Barrier Discharge (DBD plasma reactor were studied. The study was focused on finding possible reaction mechanism route during plasma electro-catalysis process. The prediction was performed based on the changes of Gas Chromatography Mass Spectrometer (GC-MS and Fourier Transform Infra Red (FT-IR analyses to the biodiesel products with respect to time length of plasma treatment. It was found that main reaction mechanism occurred in the plasma electro-catalysis system was non-thermal pyrolysis rather than transesterification. The main reactions within the plasma treatment were due to collision between high energetic electrons (supplied from high voltage power supply through high voltage electrode and the reaction mixtures. The high energetic electrons affected the electrons pair of covalent bonding to be excited or dissociated even ionized at higher energy. Therefore, this plasma electro-catalysis system was promising for biodiesel synthesis from vegetable oils due to only very short time reaction was needed, even no need a catalyst, no soap formation, and no glycerol by-product. This system could produce fatty acid methyl ester yield of 75.65% at 120 seconds and other possible chemicals, such as alkynes, alkanes, esters, carboxylic acid, and aldehydes. However, during the plasma process, the reaction mechanisms were still difficult to be controlled due the action of available high energetic electrons. The advanced studies on how to control the reaction mechanism selectively in the plasma electro-catalysis will be published elsewhere. © 2014 BCREC UNDIP. All rights reservedReceived: 23rd January 2014; Revised: 20th March 2014; Accepted: 23rd March 2014[How to Cite: Istadi, I., Yudhistira, A.D., Anggoro, D.D., Buchori, L. (2014. Electro-Catalysis System for Biodiesel Synthesis from Palm Oil over Dielectric-Barrier Discharge Plasma Reactor

Endoscopy and homogeneous-heterogeneous reactions in MHD radiative peristaltic activity of Ree-Eyring fluid

Science.gov (United States)

Hayat, Tasawar; Akram, Javaria; Alsaedi, Ahmed; Zahir, Hina

2018-03-01

Endoscopic and homogeneous-heterogeneous reactions in MHD peristalsis of Ree-Eyring fluid are addressed. Mathematical modeling and analysis have been performed by utilizing cylindrical coordinates. Nonlinear thermal radiation is present. Impact of slip boundary conditions on temperature and velocity on outer tube are taken into consideration. Lubrication approach is employed. The nonlinear system is executed numerically for solutions of velocity, temperature and concentration. Graphical results are obtained to predict physical interpretation of various embedded parameters. It is noted that homogeneous and heterogeneous reactions affect the concentration alternatively. Moreover Brinkman number rises the temperature and heat transfer coefficient whereas thermal slip drops temperature and heat transfer rate.

Darcy-Forchheimer flow with Cattaneo-Christov heat flux and homogeneous-heterogeneous reactions.

Science.gov (United States)

Hayat, Tasawar; Haider, Farwa; Muhammad, Taseer; Alsaedi, Ahmed

2017-01-01

Here Darcy-Forchheimer flow of viscoelastic fluids has been analyzed in the presence of Cattaneo-Christov heat flux and homogeneous-heterogeneous reactions. Results for two viscoelastic fluids are obtained and compared. A linear stretching surface has been used to generate the flow. Flow in porous media is characterized by considering the Darcy-Forchheimer model. Modified version of Fourier's law through Cattaneo-Christov heat flux is employed. Equal diffusion coefficients are employed for both reactants and auto catalyst. Optimal homotopy scheme is employed for solutions development of nonlinear problems. Solutions expressions of velocity, temperature and concentration fields are provided. Skin friction coefficient and heat transfer rate are computed and analyzed. Here the temperature and thermal boundary layer thickness are lower for Cattaneo-Christov heat flux model in comparison to classical Fourier's law of heat conduction. Moreover, the homogeneous and heterogeneous reactions parameters have opposite behaviors for concentration field.

Asymmetric cation-binding catalysis

DEFF Research Database (Denmark)

Oliveira, Maria Teresa; Lee, Jiwoong

2017-01-01

The employment of metal salts is quite limited in asymmetric catalysis, although it would provide an additional arsenal of safe and inexpensive reagents to create molecular functions with high optical purity. Cation chelation by polyethers increases the salts' solubility in conventional organic...... solvents, thus increasing their applicability in synthesis. The expansion of this concept to chiral polyethers led to the emergence of asymmetric cation-binding catalysis, where chiral counter anions are generated from metal salts, particularly using BINOL-based polyethers. Alkali metal salts, namely KF...... highly enantioselective silylation reactions in polyether-generated chiral environments, and leading to a record-high turnover in asymmetric organocatalysis. This can lead to further applications by the asymmetric use of other inorganic salts in various organic transformations....

Allergic reactions to raw, pasteurized, and homogenized/pasteurized cow milk

DEFF Research Database (Denmark)

Høst, A; Samuelsson, E G

1988-01-01

Five children aged 12-40 months with IgE-mediated adverse reactions to cow milk (immediate onset clinical pattern of cow milk allergy) were orally challenged double-blind in random order with three different milk preparations processed from the same batch of milk 1) raw untreated cow milk, 2......) pasteurized cow milk, 3) homogenized and pasteurized cow milk, and 4) Nutramigen (a commercial hypoallergenic infant formula based on hydrolysed casein) as placebo. Skin prick tests with the same preparations were also performed. On oral challenge the three different processed milk types provoked significant...... and similar allergic reactions in each child, and no adverse reactions followed the challenge with placebo (Nutramigen). Skin prick test with the same milk products were positive in all children and comparable to the results with an extract of purified raw cow milk protein (Soluprick), whereas Nutramigen did...

HRSSA – Efficient hybrid stochastic simulation for spatially homogeneous biochemical reaction networks

International Nuclear Information System (INIS)

Marchetti, Luca; Priami, Corrado; Thanh, Vo Hong

2016-01-01

This paper introduces HRSSA (Hybrid Rejection-based Stochastic Simulation Algorithm), a new efficient hybrid stochastic simulation algorithm for spatially homogeneous biochemical reaction networks. HRSSA is built on top of RSSA, an exact stochastic simulation algorithm which relies on propensity bounds to select next reaction firings and to reduce the average number of reaction propensity updates needed during the simulation. HRSSA exploits the computational advantage of propensity bounds to manage time-varying transition propensities and to apply dynamic partitioning of reactions, which constitute the two most significant bottlenecks of hybrid simulation. A comprehensive set of simulation benchmarks is provided for evaluating performance and accuracy of HRSSA against other state of the art algorithms.

HRSSA – Efficient hybrid stochastic simulation for spatially homogeneous biochemical reaction networks

Energy Technology Data Exchange (ETDEWEB)

Marchetti, Luca, E-mail: marchetti@cosbi.eu [The Microsoft Research – University of Trento Centre for Computational and Systems Biology (COSBI), Piazza Manifattura, 1, 38068 Rovereto (Italy); Priami, Corrado, E-mail: priami@cosbi.eu [The Microsoft Research – University of Trento Centre for Computational and Systems Biology (COSBI), Piazza Manifattura, 1, 38068 Rovereto (Italy); University of Trento, Department of Mathematics (Italy); Thanh, Vo Hong, E-mail: vo@cosbi.eu [The Microsoft Research – University of Trento Centre for Computational and Systems Biology (COSBI), Piazza Manifattura, 1, 38068 Rovereto (Italy)

2016-07-15

This paper introduces HRSSA (Hybrid Rejection-based Stochastic Simulation Algorithm), a new efficient hybrid stochastic simulation algorithm for spatially homogeneous biochemical reaction networks. HRSSA is built on top of RSSA, an exact stochastic simulation algorithm which relies on propensity bounds to select next reaction firings and to reduce the average number of reaction propensity updates needed during the simulation. HRSSA exploits the computational advantage of propensity bounds to manage time-varying transition propensities and to apply dynamic partitioning of reactions, which constitute the two most significant bottlenecks of hybrid simulation. A comprehensive set of simulation benchmarks is provided for evaluating performance and accuracy of HRSSA against other state of the art algorithms.

Organometallic chemistry of bimetallic compounds. Progress report, January 1992--July 1995

International Nuclear Information System (INIS)

Casey, C.P.

1994-07-01

Four main projects at the interface between organometallic chemistry and homogeneous catalysis were pursued. All were designed to give increased understanding of the mechanisms of organometallic reactions related to homogeneous and heterogeneous catalysis. In addition, a minor study involving η 5 -to η 1 -cyclopentadienyl ring slippage in catalysis was completed

A General Ligand Design for Gold Catalysis allowing Ligand-Directed Anti Nucleophilic Attack of Alkynes

Science.gov (United States)

Wang, Yanzhao; Wang, Zhixun; Li, Yuxue; Wu, Gongde; Cao, Zheng; Zhang, Liming

2014-01-01

Most homogenous gold catalyses demand ≥0.5 mol % catalyst loading. Due to the high cost of gold, these reactions are unlikely to be applicable in medium or large scale applications. Here we disclose a novel ligand design based on the privileged biphenyl-2-phosphine framework that offers a potentially general approach to dramatically lowering catalyst loading. In this design, an amide group at the 3’ position of the ligand framework directs and promotes nucleophilic attack at the ligand gold complex-activated alkyne, which is unprecedented in homogeneous gold catalysis considering the spatial challenge of using ligand to reach antiapproaching nucleophile in a linear P-Au-alkyne centroid structure. With such a ligand, the gold(I) complex becomes highly efficient in catalyzing acid addition to alkynes, with a turnover number up to 99,000. Density functional theory calculations support the role of the amide moiety in directing the attack of carboxylic acid via hydrogen bonding. PMID:24704803

Organometallic chemistry of bimetallic compounds. Progress report, January 1992--July 1995

Energy Technology Data Exchange (ETDEWEB)

Casey, C.P.

1994-07-01

Four main projects at the interface between organometallic chemistry and homogeneous catalysis were pursued. All were designed to give increased understanding of the mechanisms of organometallic reactions related to homogeneous and heterogeneous catalysis. In addition, a minor study involving {eta}{sup 5}-to {eta}{sup 1}-cyclopentadienyl ring slippage in catalysis was completed.

Polymer-silica hybrids for separation of CO2 and catalysis of organic reactions

Science.gov (United States)

Silva Mojica, Ernesto

Porous materials comprising polymeric and inorganic segments have attracted interest from the scientific community due to their unique properties and functionalities. The physical and chemical characteristics of these materials can be effectively exploited for adsorption applications. This dissertation covers the experimental techniques for fabrication of poly(vinyl alcohol) (PVA) and silica (SiO2) porous supports, and their functionalization with polyamines for developing adsorbents with potential applications in separation of CO2 and catalysis of organic reactions. The supports were synthesized by processes involving (i) covalent cross-linking of PVA, (ii) hydrolysis and poly-condensation of silica precursors (i,e,. sol-gel synthesis), and formation of porous structures via (iii) direct templating and (iv) phase inversion techniques. Their physical structure was controlled by the proper combination of the preparation procedures, which resulted in micro-structured porous materials in the form of micro-particles, membranes, and pellets. Their adsorption characteristics were tailored by functionalization with polyethyleneimine (PEI), and their physicochemical properties were characterized by vibrational spectroscopy (FTIR, UV-vis), microscopy (SEM), calorimetry (TGA, DSC), and adsorption techniques (BET, step-switch adsorption). Spectroscopic investigations of the interfacial cross-linking reactions of PEI and PVA with glutaraldehyde (GA) revealed that PEI catalyzes the cross-linking reactions of PVA in absence of external acid catalysts. In-situ IR spectroscopy coupled with a focal plane array (FPA) image detector allowed the characterization of a gradient interface on a PEI/PVA composite membrane and the investigation of the cross-linking reactions as a function of time and position. The results served as a basis to postulate possible intermediates, and propose the reaction mechanisms. The formulation of amine-functionalized CO2 capture sorbents was based on the

Catalysis studies

International Nuclear Information System (INIS)

Taylor, T.N.; Ellis, W.P.

1977-11-01

The New Research Initiatives Program (NRIP) project on catalysis in Los Alamos Scientific Laboratory (LASL) Group CMB-8 has made significant progress towards performing the first basic in situ experimental studies of heterogeneous catalysis on solid compound surfaces in a LEED-Auger system. To further understand the surface crystallography of a possible catalyst compound, LEED-Auger measurements were made on UO 2 (approximately 100) vicinal surfaces. These (approximately 100) vicinal surfaces were shown to decompose irreversibly into lower index facets, including prominent (100) facets, at temperatures below those needed for creation of lowest index faceting on (approximately 111) vicinal surfaces. LEED examination of fully faceted surfaces from both types of UO 2 vicinal cuts did not show evidence of cyclopropane or propene chemisorption. The existing LEED-Auger system was modified to allow catalytic reactions at approximately less than 10 -3 torr. A sample holder, specifically designed for catalysis measurements in the modified system, was tested while examining single crystals of CoO and Cr 2 O 3 . Extensive LEED-Auger measurements were made on CoO in vacuo and in the presence of light hydrocarbons and alcohols plus H 2 O, NO, and NH 3 . No chemisorptive behavior was observed except with H 2 O in the presence of the electron beam. Although only examined briefly, the Cr 2 O 3 was remarkable for the sharp LEED features obtained prior to any surface treatment in the vacuum system

Transition metal catalysis in confined spaces

NARCIS (Netherlands)

Leenders, S.H.A.M.

2016-01-01

Chemical reactions are required for the conversion of feedstocks to valuable materials, such as different types of plastics, pharmaceutical ingredients and advanced materials. In order to facilitate the conversion of these feedstocks to a wide array of products, catalysis plays a prominent role.

Molecular complexity from polyunsaturated substrates: the gold catalysis approach.

Science.gov (United States)

Fensterbank, Louis; Malacria, Max

2014-03-18

Over the last two decades, electrophilic catalysis relying on platinum(II), gold(I), and gold(III) salts has emerged as a remarkable synthetic methodology. Chemists have discovered a large variety of organic transformations that convert a great assortment of highly functionalized precursors into valuable final products. In many cases, these methodologies offer unique features, allowing access to unprecedented molecular architectures. Due to the mild reaction conditions and high function compatibility, scientists have successfully developed applications in total synthesis of natural products, as well as in asymmetric catalysis. In addition, all these developments have been accompanied by the invention of well-tailored catalysts, so that a palette of different electrophilic agents is now commercially available or readily synthesized at the bench. In some respects, researchers' interests in developing homogeneous gold catalysis can be compared with the Californian gold rush of the 19th century. It has attracted into its fervor thousands of scientists, providing a huge number of versatile and important reports. More notably, it is clear that the contribution to the art of organic synthesis is very valuable, though the quest is not over yet. Because they rely on the intervention of previously unknown types of intermediates, new retrosynthetic disconnections are now possible. In this Account, we discuss our efforts on the use of readily available polyunsaturated precursors, such as enynes, dienynes, allenynes, and allenenes to give access to highly original polycyclic structures in a single operation. These transformations transit via previously undescribed intermediates A, B, D, F, and H that will be encountered later on. All these intermediates have been determined by both ourselves and others by DFT calculations and in some cases have been confirmed on the basis of experimental data. In addition, dual gold activation can be at work in some of these transformations

Cooperative catalysis by silica-supported organic functional groups

OpenAIRE

Margelefsky, Eric L.; Zeidan, Ryan K.; Davis, Mark E.

2008-01-01

Hybrid inorganic–organic materials comprising organic functional groups tethered from silica surfaces are versatile, heterogeneous catalysts. Recent advances have led to the preparation of silica materials containing multiple, different functional groups that can show cooperative catalysis; that is, these functional groups can act together to provide catalytic activity and selectivity superior to what can be obtained from either monofunctional materials or homogeneous catalysts. This tutorial...

Catalysis by nonmetals rules for catalyst selection

CERN Document Server

Krylov, Oleg V

1970-01-01

Catalysis by Non-metals: Rules of Catalyst Selection presents the development of scientific principles for the collection of catalysts. It discusses the investigation of the mechanism of chemosorption and catalysis. It addresses a series of properties of solid with catalytic activity. Some of the topics covered in the book are the properties of a solid and catalytic activity in oxidation-reduction reactions; the difference of electronegativities and the effective charges of atoms; the role of d-electrons in the catalytic properties of a solid; the color of solids; and proton-acid and proton-ba

Outcome of homogeneous and heterogeneous reactions in Darcy-Forchheimer flow with nonlinear thermal radiation and convective condition

Science.gov (United States)

Hayat, T.; Shah, Faisal; Alsaedi, A.; Hussain, Zakir

The present analysis aims to report the consequences of nonlinear radiation, convective condition and heterogeneous-homogeneous reactions in Darcy-Forchheimer flow over a non-linear stretching sheet with variable thickness. Non-uniform magnetic field and nonuniform heat generation/absorption are accounted. The governing boundary layer partial differential equations are converted into a system of nonlinear ordinary differential equations. The computations are organized and the effects of physical variables such as thickness parameter, power index, Hartman number, inertia and porous parameters, radiation parameter, Biot number, Prandtl number, ratio parameter, heat generation parameter and homogeneous-heterogeneous reaction parameter are investigated. The variations of skin friction coefficient and Nusselt number for different interesting variables are plotted and discussed. It is noticed that Biot number and heat generation variable lead to enhance the temperature distribution. The solutal boundary layer thickness decreases for larger homogeneous variable while reverse trend is seen for heterogeneous reaction.

Challenges and perspectives for catalysis in production of diesel from biomass

DEFF Research Database (Denmark)

Madsen, Anders Theilgaard; Søndergaard, Helle; Fehrmann, Rasmus

2011-01-01

oils or waste fats with methanol is the most prominent and has been applied industrially for a decade. Homogeneous acid and base catalysis is normally used, but solid acids, solid bases, ionic liquids and lipases are being developed as replacements. Hydrodeoxygenation of vegetable oils has likewise...

Supported ionic liquid-phase (SILP) catalysis

DEFF Research Database (Denmark)

Riisager, Anders; Fehrmann, Rasmus; Wasserscheid, P.

2005-01-01

The concept of supported ionic liquid-phase (SILP) catalysis has been demonstrated for gas- and liquid-phase continuous fixed-bed reactions using rhodium phosphine catalyzed hydroformylation of propene and 1-octene as examples. The nature of the support had important influence on both the catalytic...

Mineral catalysis of oil producing reactions in coal liquefaction

Energy Technology Data Exchange (ETDEWEB)

Shridharani, K.G.

1983-01-01

This work was concerned primarily with the development of a relatively inexpensive, readily available, high activity catalyst that can be used as a disposable catalyst in coal liquefaction processes. For a fair evaluation of the developmental mineral catalyst (presulfided iron oxide), it was necessary to determine at different stages of this work, whether catalyst inhibition, deactivation or activity was the limiting factor in coal liquefaction catalysis. First, different routes were explored to prepare a high hydrogenation activity, iron-based catalyst. Naphthalene hydrogenation was used as a model reaction to rate the hydrogenation activities of different additives. Presulfiding of iron oxide with H/sub 2/S, under controlled conditions, rendered the highest hydrogenation activity mineral catalyst, which had a hydrogenation activity even greater than that of commercial CoMo/Al/sub 2/O/sub 3/ catalyst sulfided with creosote oil and hydrogen. Sulfiding of CoMo/Al/sub 2/O/sub 3/ catalyst with H/sub 2/S remarkably improved its initial hydrogenation activity. Second, the catalyst inhibition and deactivation during liquefaction were studied. Liquefaction-process solvents contain a number of compounds that can either deactivate or inhibit the hydrogenation activity of a catalyst. Finally, the hydrocracking activity of the presulfided iron oxide catalyst was compared with that of commercial catalysts, CoMo/Al/sub 2/O/sub 3/ and low alumina FCC catalyst.

Survey on synthesis and reaction of environmentally benign water-soluble metal complex catalysts; Kankyo chowagata suiyosei sakutai shokubai no gosei hanno no chosa

Energy Technology Data Exchange (ETDEWEB)

NONE

1997-03-01

This report describes the research trend survey results on the synthesis and reaction of water-soluble metal complexes which are regarded as environmentally benign catalysts. For the synthesis and catalysis of water-soluble complexes, synthetic methods of water-soluble phosphines, such as sulfonated TPPMS and TPPTS, are described in detail. Synthesis and reactivity of hydroxymethylphosphines are introduced, and the application of electrospray mass spectroscopy is elucidated as a tool for the analysis of them. Changes of the application of transition metal complexes with water-soluble phosphines to catalysis are described. Dual catalysts which have both functions of phase transfer catalysts and homogeneous catalysts are introduced. Concept of counter phase transfer catalysts is also introduced, and some catalytic reactions are described. In addition, this report introduces catalysis of water-soluble polymer-supported metal complexes, immobilization of metal colloids with water-soluble ligands and their analysis, and water-soluble complexes as hybrid catalysts. 144 refs., 94 figs., 10 tabs.

Anion-π Catalysis of Enolate Chemistry: Rigidified Leonard Turns as a General Motif to Run Reactions on Aromatic Surfaces.

Science.gov (United States)

Cotelle, Yoann; Benz, Sebastian; Avestro, Alyssa-Jennifer; Ward, Thomas R; Sakai, Naomi; Matile, Stefan

2016-03-18

To integrate anion-π, cation-π, and ion pair-π interactions in catalysis, the fundamental challenge is to run reactions reliably on aromatic surfaces. Addressing a specific question concerning enolate addition to nitroolefins, this study elaborates on Leonard turns to tackle this problem in a general manner. Increasingly refined turns are constructed to position malonate half thioesters as close as possible on π-acidic surfaces. The resulting preorganization of reactive intermediates is shown to support the disfavored addition to enolate acceptors to an absolutely unexpected extent. This decisive impact on anion-π catalysis increases with the rigidity of the turns. The new, rigidified Leonard turns are most effective with weak anion-π interactions, whereas stronger interactions do not require such ideal substrate positioning to operate well. The stunning simplicity of the motif and its surprisingly strong relevance for function should render the introduced approach generally useful. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Kinetic evolutionary behavior of catalysis-select migration

International Nuclear Information System (INIS)

Wu Yuan-Gang; Lin Zhen-Quan; Ke Jian-Hong

2012-01-01

We propose a catalysis-select migration driven evolution model of two-species (A- and B-species) aggregates, where one unit of species A migrates to species B under the catalysts of species C, while under the catalysts of species D the reaction will become one unit of species B migrating to species A. Meanwhile the catalyst aggregates of species C perform self-coagulation, as do the species D aggregates. We study this catalysis-select migration driven kinetic aggregation phenomena using the generalized Smoluchowski rate equation approach with C species catalysis-select migration rate kernel K(k;i,j) = Kkij and D species catalysis-select migration rate kernel J(k;i,j)= Jkij. The kinetic evolution behaviour is found to be dominated by the competition between the catalysis-select immigration and emigration, in which the competition is between JD 0 and KC 0 (D 0 and C 0 are the initial numbers of the monomers of species D and C, respectively). When JD 0 −KC 0 > 0, the aggregate size distribution of species A satisfies the conventional scaling form and that of species B satisfies a modified scaling form. And in the case of JD 0 −KC 0 0 −KC 0 > 0 case. (interdisciplinary physics and related areas of science and technology)

Water oxidation catalysis with nonheme iron complexes under acidic and basic conditions: homogeneous or heterogeneous?

Science.gov (United States)

Hong, Dachao; Mandal, Sukanta; Yamada, Yusuke; Lee, Yong-Min; Nam, Wonwoo; Llobet, Antoni; Fukuzumi, Shunichi

2013-08-19

Thermal water oxidation by cerium(IV) ammonium nitrate (CAN) was catalyzed by nonheme iron complexes, such as Fe(BQEN)(OTf)2 (1) and Fe(BQCN)(OTf)2 (2) (BQEN = N,N'-dimethyl-N,N'-bis(8-quinolyl)ethane-1,2-diamine, BQCN = N,N'-dimethyl-N,N'-bis(8-quinolyl)cyclohexanediamine, OTf = CF3SO3(-)) in a nonbuffered aqueous solution; turnover numbers of 80 ± 10 and 20 ± 5 were obtained in the O2 evolution reaction by 1 and 2, respectively. The ligand dissociation of the iron complexes was observed under acidic conditions, and the dissociated ligands were oxidized by CAN to yield CO2. We also observed that 1 was converted to an iron(IV)-oxo complex during the water oxidation in competition with the ligand oxidation. In addition, oxygen exchange between the iron(IV)-oxo complex and H2(18)O was found to occur at a much faster rate than the oxygen evolution. These results indicate that the iron complexes act as the true homogeneous catalyst for water oxidation by CAN at low pHs. In contrast, light-driven water oxidation using [Ru(bpy)3](2+) (bpy = 2,2'-bipyridine) as a photosensitizer and S2O8(2-) as a sacrificial electron acceptor was catalyzed by iron hydroxide nanoparticles derived from the iron complexes under basic conditions as the result of the ligand dissociation. In a buffer solution (initial pH 9.0) formation of the iron hydroxide nanoparticles with a size of around 100 nm at the end of the reaction was monitored by dynamic light scattering (DLS) in situ and characterized by X-ray photoelectron spectra (XPS) and transmission electron microscope (TEM) measurements. We thus conclude that the water oxidation by CAN was catalyzed by short-lived homogeneous iron complexes under acidic conditions, whereas iron hydroxide nanoparticles derived from iron complexes act as a heterogeneous catalyst in the light-driven water oxidation reaction under basic conditions.

Highly Dispersed Pseudo-Homogeneous and Heterogeneous Catalysts Synthesized via Inverse Micelle Solutions for the Liquefaction of Coal

Energy Technology Data Exchange (ETDEWEB)

Hampden-Smith, M.; Kawola, J.S.; Martino, A.; Sault, A.G.; Yamanaka, S.A.

1999-01-05

The mission of this project was to use inverse micelle solutions to synthesize nanometer sized metal particles and test the particles as catalysts in the liquefaction of coal and other related reactions. The initial focus of the project was the synthesis of iron based materials in pseudo-homogeneous form. The frost three chapters discuss the synthesis, characterization, and catalyst testing in coal liquefaction and model coal liquefaction reactions of iron based pseudo-homogeneous materials. Later, we became interested in highly dispersed catalysts for coprocessing of coal and plastic waste. Bifunctional catalysts . to hydrogenate the coal and depolymerize the plastic waste are ideal. We began studying, based on our previously devised synthesis strategies, the synthesis of heterogeneous catalysts with a bifunctional nature. In chapter 4, we discuss the fundamental principles in heterogeneous catalysis synthesis with inverse micelle solutions. In chapter 5, we extend the synthesis of chapter 4 to practical systems and use the materials in catalyst testing. Finally in chapter 6, we return to iron and coal liquefaction now studied with the heterogeneous catalysts.

A spectral study of the elementary step of proton transfer in heterogeneous acid catalysis

Energy Technology Data Exchange (ETDEWEB)

Kazanskii, V B

1977-09-01

A spectral study of the elementary step of proton transfer in heterogeneous acid catalysis involved a determination of the potential curves of the OH bond in surface hydroxyl groups (e.g., those on silica, NaHY zeolite, or glass) of differing acidity from IR stretching frequency data in the overtone region; a calculation of the activation energies for proton transfer during acid catalysis from the changes in the curve forms after adsorption of various molecules (e.g., water, ammonia, benzene, toluene, xylenes, acetone, and cyclohexane); and a comparison of the IR predictions with quantum-chemical calculations of the potential curves. The results appear to furnish a new criterion for the coordinate of reactions involving Broensted sites: if the activation energy measured during actual catalysis is close to that calculated from the IR stretching data, the reaction proceeds by the stepwise mechanism of acid catalysis; but if these values differ greatly, the reaction involves a concerted mechanism (i.e., activation of the adsorbed molecule without involvement of OH groups). Tables, graphs, and 15 references.

Catalysis by Design: Well-Defined Single-Site Heterogeneous Catalysts

KAUST Repository

Pelletier, Jeremie

2016-03-09

ConspectusHeterogeneous catalysis, a field important industrially and scientifically, is increasingly seeking and refining strategies to render itself more predictable. The main issue is due to the nature and the population of catalytically active sites. Their number is generally low to very low, their "acid strengths" or " redox properties" are not homogeneous, and the material may display related yet inactive sites on the same material. In many heterogeneous catalysts, the discovery of a structure-activity reationship is at best challenging. One possible solution is to generate single-site catalysts in which most, if not all, of the sites are structurally identical. Within this context and using the right tools, the catalyst structure can be designed and well-defined, to reach a molecular understanding. It is then feasible to understand the structure-activity relationship and to develop predictable heterogeneous catalysis. Single-site well-defined heterogeneous catalysts can be prepared using concepts and tools of surface organometallic chemistry (SOMC). This approach operates by reacting organometallic compounds with surfaces of highly divided oxides (or of metal nanoparticles). This strategy has a solid track record to reveal structure-activity relationship to the extent that it is becoming now quite predictable. Almost all elements of the periodical table have been grafted on surfaces of oxides (from simple oxides such as silica or alumina to more sophisticated materials regarding composition or porosity).Considering catalytic hydrocarbon transformations, heterogeneous catalysis outcome may now be predicted based on existing mechanistic proposals and the rules of molecular chemistry (organometallic, organic) associated with some concepts of surface sciences. A thorough characterization of the grafted metal centers must be carried out using tools spanning from molecular organometallic or surface chemistry. By selection of the metal, its ligand set, and the

In-situ nanoelectrospray for high-throughput screening of enzymes and real-time monitoring of reactions.

Science.gov (United States)

Yang, Yuhan; Han, Feifei; Ouyang, Jin; Zhao, Yunling; Han, Juan; Na, Na

2016-01-01

The in-situ and high-throughput evaluation of enzymes and real-time monitoring of enzyme catalyzed reactions in liquid phase is quite significant in the catalysis industry. In-situ nanoelectrospray, the direct sampling and ionization method for mass spectrometry, has been applied for high-throughput evaluation of enzymes, as well as the on-line monitoring of reactions. Simply inserting a capillary into a liquid system with high-voltage applied, analytes in liquid reaction system can be directly ionized at the capillary tip with small volume consumption. With no sample pre-treatment or injection procedure, different analytes such as saccharides, amino acids, alkaloids, peptides and proteins can be rapidly and directly extracted from liquid phase and ionized at the capillary tip. Taking irreversible transesterification reaction of vinyl acetate and ethanol as an example, this technique has been used for the high-throughput evaluation of enzymes, fast optimizations, as well as real-time monitoring of reaction catalyzed by different enzymes. In addition, it is even softer than traditional electrospray ionization. The present method can also be used for the monitoring of other homogenous and heterogeneous reactions in liquid phases, which will show potentials in the catalysis industry. Copyright © 2015 Elsevier B.V. All rights reserved.

Heterogenization of Homogeneous Catalysts: the Effect of the Support

Energy Technology Data Exchange (ETDEWEB)

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

1999-06-29

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

Enzyme-Like Catalysis of the Nazarov Cyclization by Supramolecular Encapsulation

Energy Technology Data Exchange (ETDEWEB)

Hastings, Courtney; Pluth, Michael; Bergman, Robert; Raymond, Kenneth

2010-03-29

A primary goal in the design and synthesis of molecular hosts has been the selective recognition and binding of a variety of guests using non-covalent interactions. Supramolecular catalysis, which is the application of such hosts towards catalysis, has much in common with many enzymatic reactions, chiefly the use of both spatially appropriate binding pockets and precisely oriented functional groups to recognize and activate specific substrate molecules. Although there are now many examples which demonstrate how selective encapsulation in a host cavity can enhance the reactivity of a bound guest, all have failed to reach the degree of increased reactivity typical of enzymes. We now report the catalysis of the Nazarov cyclization by a self-assembled coordination cage, a carbon-carbon bond-forming reaction which proceeds under mild, aqueous conditions. The acceleration in this system is over a million-fold, and represents the first example of supramolecular catalysis that achieves the level of rate enhancement comparable to that observed in several enzymes. We explain the unprecedented degree of rate increase as due to the combination of (a) preorganization of the encapsulated substrate molecule, (b) stabilization of the transition state of the cyclization by constrictive binding, and (c) increase in the basicity of the complexed alcohol functionality.

Highly Efficient Cooperative Catalysis by Co ^III (Porphyrin) Pairs in Interpenetrating Metal-Organic Frameworks

Energy Technology Data Exchange (ETDEWEB)

Lin, Zekai; Zhang, Zhi-Ming; Chen, Yu-Sheng; Lin, Wenbin (UC); (Xiamen)

2016-12-02

A series of porous twofold interpenetrated In-Co^III(porphyrin) metal–organic frameworks (MOFs) were constructed by in situ metalation of porphyrin bridging ligands and used as efficient cooperative catalysts for the hydration of terminal alkynes. The twofold interpenetrating structure brings adjacent Co^III(porphyrins) in the two networks parallel to each other with a distance of about 8.8 Å, an ideal distance for the simultaneous activation of both substrates in alkyne hydration reactions. As a result, the In-Co^III(porphyrin) MOFs exhibit much higher (up to 38 times) catalytic activity than either homogeneous catalysts or MOF controls with isolated Co^III(porphyrin) centers, thus highlighting the potential application of MOFs in cooperative catalysis.

Dedicated Beamline Facilities for Catalytic Research. Synchrotron Catalysis Consortium (SCC)

Energy Technology Data Exchange (ETDEWEB)

Chen, Jingguang [Columbia Univ., New York, NY; Frenkel, Anatoly [Yeshiva Univ., New York, NY (United States); Rodriguez, Jose [Brookhaven National Lab. (BNL), Upton, NY (United States); Adzic, Radoslav [Brookhaven National Lab. (BNL), Upton, NY (United States); Bare, Simon R. [UOP LLC, Des Plaines, IL (United States); Hulbert, Steve L. [Brookhaven National Lab. (BNL), Upton, NY (United States); Karim, Ayman [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Mullins, David R. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Overbury, Steve [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

2015-03-04

Synchrotron spectroscopies offer unique advantages over conventional techniques, including higher detection sensitivity and molecular specificity, faster detection rate, and more in-depth information regarding the structural, electronic and catalytic properties under in-situ reaction conditions. Despite these advantages, synchrotron techniques are often underutilized or unexplored by the catalysis community due to various perceived and real barriers, which will be addressed in the current proposal. Since its establishment in 2005, the Synchrotron Catalysis Consortium (SCC) has coordinated significant efforts to promote the utilization of cutting-edge catalytic research under in-situ conditions. The purpose of the current renewal proposal is aimed to provide assistance, and to develop new sciences/techniques, for the catalysis community through the following concerted efforts: Coordinating the implementation of a suite of beamlines for catalysis studies at the new NSLS-II synchrotron source; Providing assistance and coordination for catalysis users at an SSRL catalysis beamline during the initial period of NSLS to NSLS II transition; Designing in-situ reactors for a variety of catalytic and electrocatalytic studies; Assisting experimental set-up and data analysis by a dedicated research scientist; Offering training courses and help sessions by the PIs and co-PIs.

Catalysis by metallic nanoparticles in solution: Thermosensitive microgels as nanoreactors

OpenAIRE

Roa, Rafael; Angioletti-Uberti, Stefano; Lu, Yan; Dzubiella, Joachim; Piazza, Francesco; Ballauff, Matthias

2018-01-01

Metallic nanoparticles have been used as catalysts for various reactions, and the huge literature on the subject is hard to overlook. In many applications, the nanoparticles must be affixed to a colloidal carrier for easy handling during catalysis. These "passive carriers" (e.g., dendrimers) serve for a controlled synthesis of the nanoparticles and prevent coagulation during catalysis. Recently, hybrids from nanoparticles and polymers have been developed that allow us to change the catalytic ...

An improved stochastic algorithm for temperature-dependent homogeneous gas phase reactions

CERN Document Server

Kraft, M

2003-01-01

We propose an improved stochastic algorithm for temperature-dependent homogeneous gas phase reactions. By combining forward and reverse reaction rates, a significant gain in computational efficiency is achieved. Two modifications of modelling the temperature dependence (with and without conservation of enthalpy) are introduced and studied quantitatively. The algorithm is tested for the combustion of n-heptane, which is a reference fuel component for internal combustion engines. The convergence of the algorithm is studied by a series of numerical experiments and the computational cost of the stochastic algorithm is compared with the DAE code DASSL. If less accuracy is needed the stochastic algorithm is faster on short simulation time intervals. The new stochastic algorithm is significantly faster than the original direct simulation algorithm in all cases considered.

Advances in catalysis

CERN Document Server

Gates, Bruce C

2012-01-01

Advances in Catalysis fills the gap between the journal papers and the textbooks across the diverse areas of catalysis research. For more than 60 years Advances in Catalysis has been dedicated to recording progress in the field of catalysis and providing the scientific community with comprehensive and authoritative reviews. This series in invaluable to chemical engineers, physical chemists, biochemists, researchers and industrial chemists working in the fields of catalysis and materials chemistry. * In-depth, critical, state-of-the-art reviews * Comprehensive, covers of all as

Rate tracer studies of heterogeneous catalysis

Energy Technology Data Exchange (ETDEWEB)

Happel, J; Kiang, S

1977-10-01

An analysis is presented of the extent to which parameters involved in transient tracing of isotopic species in heterogeneous catalysis can be determined by experiments in which tracer concentrations are measured as a function of time. Different treatments for open and closed systems with the over-all reaction at equilibrium or irreversible were developed.

Organocatalysis: Fundamentals and Comparisons to Metal and Enzyme Catalysis

Directory of Open Access Journals (Sweden)

Pierre Vogel

2016-08-01

Full Text Available Catalysis fulfills the promise that high-yielding chemical transformations will require little energy and produce no toxic waste. This message is carried by the study of the evolution of molecular catalysis of some of the most important reactions in organic chemistry. After reviewing the conceptual underpinnings of catalysis, we discuss the applications of different catalysts according to the mechanism of the reactions that they catalyze, including acyl group transfers, nucleophilic additions and substitutions, and C–C bond forming reactions that employ umpolung by nucleophilic additions to C=O and C=C double bonds. We highlight the utility of a broad range of organocatalysts other than compounds based on proline, the cinchona alkaloids and binaphthyls, which have been abundantly reviewed elsewhere. The focus is on organocatalysts, although a few examples employing metal complexes and enzymes are also included due to their significance. Classical Brønsted acids have evolved into electrophilic hands, the fingers of which are hydrogen donors (like enzymes or other electrophilic moieties. Classical Lewis base catalysts have evolved into tridimensional, chiral nucleophiles that are N- (e.g., tertiary amines, P- (e.g., tertiary phosphines and C-nucleophiles (e.g., N-heterocyclic carbenes. Many efficient organocatalysts bear electrophilic and nucleophilic moieties that interact simultaneously or not with both the electrophilic and nucleophilic reactants. A detailed understanding of the reaction mechanisms permits the design of better catalysts. Their construction represents a molecular science in itself, suggesting that sooner or later chemists will not only imitate Nature but be able to catalyze a much wider range of reactions with high chemo-, regio-, stereo- and enantioselectivity. Man-made organocatalysts are much smaller, cheaper and more stable than enzymes.

Oxygen evolution reaction catalysis

Energy Technology Data Exchange (ETDEWEB)

Haber, Joel A.; Jin, Jian; Xiang, Chengxiang; Gregoire, John M.; Jones, Ryan J.; Guevarra, Dan W.; Shinde, Aniketa A.

2016-09-06

An Oxygen Evolution Reaction (OER) catalyst includes a metal oxide that includes oxygen, cerium, and one or more second metals. In some instances, the cerium is 10 to 80 molar % of the metals in the metal oxide and/or the catalyst includes two or more second metals. The OER catalyst can be included in or on an electrode. The electrode can be arranged in an oxygen evolution system such that the Oxygen Evolution Reaction occurs at the electrode.

Catalysis in the Service of Green Chemistry: Nobel Prize-Winning Palladium-Catalysed Cross-Couplings, Run in Water at Room Temperature: Heck, Suzuki-Miyaura and Negishi reactions carried out in the absence of organic solvents, enabled by micellar catalysis.

Science.gov (United States)

Lipshutz, Bruce H; Taft, Benjamin R; Abela, Alexander R; Ghorai, Subir; Krasovskiy, Arkady; Duplais, Christophe

2012-04-01

Palladium-catalysed cross-couplings, in particular Heck, Suzuki-Miyaura and Negishi reactions developed over three decades ago, are routinely carried out in organic solvents. However, alternative media are currently of considerable interest given an increasing emphasis on making organic processes 'greener'; for example, by minimising organic waste in the form of organic solvents. Water is the obvious leading candidate in this regard. Hence, this review focuses on the application of micellar catalysis, in which a 'designer' surfactant enables these award-winning coupling reactions to be run in water at room temperature.

Impact of Secondary Interactions in Asymmetric Catalysis

OpenAIRE

Frölander, Anders

2007-01-01

This thesis deals with secondary interactions in asymmetric catalysis and their impact on the outcome of catalytic reactions. The first part revolves around the metal-catalyzed asymmetric allylic alkylation reaction and how interactions within the catalyst affect the stereochemistry. An OH–Pd hydrogen bond in Pd(0)–π-olefin complexes of hydroxy-containing oxazoline ligands was identified by density functional theory computations and helped to rationalize the contrasting results obtained emplo...

Nano-catalysts: Bridging the gap between homogeneous and heterogeneous catalysis

Science.gov (United States)

Functionalized nanoparticles have emerged as sustainable alternatives to conventional materials, as robust, high-surface-area heterogeneous catalyst supports. We envisioned a catalyst system, which can bridge the homogenous and heterogeneous system. Postsynthetic surface modifica...

Uma perspectiva computacional sobre catálise enzimática A computational perspective on enzymatic catalysis

Directory of Open Access Journals (Sweden)

Guilherme M. Arantes

2008-01-01

Full Text Available Enzymes are extremely efficient catalysts. Here, part of the mechanisms proposed to explain this catalytic power will be compared to quantitative experimental results and computer simulations. Influence of the enzymatic environment over species along the reaction coordinate will be analysed. Concepts of transition state stabilisation and reactant destabilisation will be confronted. Divided site model and near-attack conformation hypotheses will also be discussed. Molecular interactions such as covalent catalysis, general acid-base catalysis, electrostatics, entropic effects, steric hindrance, quantum and dynamical effects will also be analysed as sources of catalysis. Reaction mechanisms, in particular that catalysed by protein tyrosine phosphatases, illustrate the concepts.

Reactions homogenes en phase gazeuse dans les lits fluidises

Science.gov (United States)

Laviolette, Jean-Philippe

This thesis presents a study on homogeneous gas-phase reactions in fluidized beds. The main objective is to develop new tools to model and characterize homogeneous gas-phase reactions in this type of reactor. In the first part of this work, the non-premixed combustion of C 1 to C4 n-alkanes with air was investigated inside a bubbling fluidized bed of inert sand particles at intermediate temperatures: 923 K ≤ TB ≤ 1123 K. For ethane, propane and n-butane, combustion occurred mainly in the freeboard region at bed temperatures below T1 = 923 K. On the other hand, complete conversion occurred within 0.2 m of the injector at: T2 = 1073 K. For methane, the measured values of T1 and T2 were significantly higher at 1023 K and above 1123 K, respectively. The fluidized bed combustion was accurately modeled with first-order global kinetics and two one-phase PFR models in series: one PFR to model the region close to the injector and another to represent the main fluidized bed body. The measured global reaction rates for C2 to C4 n-alkanes were characterized by a uniform Arrhenius expression, while the global reaction rate for methane was significantly slower. Reactions in the injector region either led to significant conversion in that zone or an autoignition delay inside the main fluidized bed body. The conversion in the injector region increased with rising fluidized bed temperature and decreased with increasing jet velocity. To account for the promoting and inhibiting effects, an analogy was made with the concept of induction time: the PFR length (bi) of the injector region was correlated to the fluidized bed temperature and jet velocity using an Arrhenius expression. In the second part of this work, propane combustion experiments were conducted in the freeboard of a fluidized bed of sand particles at temperatures between 818 K and 923 K and at superficial gas velocity twice the minimum fluidization velocity. The freeboard region was characterized by simultaneous

Magnetic catalysis and inverse magnetic catalysis in QCD

International Nuclear Information System (INIS)

Mueller, N.

2015-01-01

We investigate the effects of strong magnetic fields on the QCD phase structure at vanishing density by solving the gluon and quark gap equations. The chiral crossover temperature as well as the chiral condensate is computed. For asymptotically large magnetic fields we find magnetic catalysis, while we find inverse magnetic catalysis for intermediate magnetic fields. Moreover, for large magnetic fields the chiral phase transition for massless quarks turns into a crossover. The underlying mechanisms are then investigated analytically within a few simplifications of the full numerical analysis. We find that a combination of gluon screening effects and the weakening of the strong coupling is responsible for the phenomenon of inverse catalysis seen in lattice studies. In turn, the magnetic catalysis at large magnetic field is already indicated by simple arguments based on dimensionality. (author)

Metal-Organic-Framework mediated supported-cobalt catalysts in multiphase hydrogenation reactions

OpenAIRE

Sun, X.

2017-01-01

The production of most industrially important chemicals involves catalysis. Depending on the difference in phases between the catalysts and reactants, one distinguishes homogenous catalysis and heterogeneous catalysis, with the latter being more attractive in real applications, due to the easy separation of products from catalysts and reusing the latter. In spite of the research and development of heterogeneous catalysts for decades, the exploration for catalysts system with outstanding activ...

Three dimensional radiative flow of magnetite-nanofluid with homogeneous-heterogeneous reactions

Science.gov (United States)

Hayat, Tasawar; Rashid, Madiha; Alsaedi, Ahmed

2018-03-01

Present communication deals with the effects of homogeneous-heterogeneous reactions in flow of nanofluid by non-linear stretching sheet. Water based nanofluid containing magnetite nanoparticles is considered. Non-linear radiation and non-uniform heat sink/source effects are examined. Non-linear differential systems are computed by Optimal homotopy analysis method (OHAM). Convergent solutions of nonlinear systems are established. The optimal data of auxiliary variables is obtained. Impact of several non-dimensional parameters for velocity components, temperature and concentration fields are examined. Graphs are plotted for analysis of surface drag force and heat transfer rate.

Molecular weight enlargement : a molecular approach to continuous homogeneous catalysis

NARCIS (Netherlands)

Janssen, M.C.C.

2010-01-01

Homogeneous catalysts play an increasingly important role in organic synthesis today, because of their high activity and selectivity. Usually, precious metals are used in combination with valuable ligands and since metal prices are expected to increase further in the future, methods for their

New Tools for CO2 Fixation by Homogeneous Catalysis - Final Technical Report

Energy Technology Data Exchange (ETDEWEB)

Jessop, Phillip G.

2006-01-20

The overall goal is the development of new or more efficient methods for the conversion of CO{sub 2} into useful organic products, via the design or discovery of new catalysts, ligands, solvents, and methods. Specific objectives for this funded period: (1) To develop a high-throughput screening technique and use it to develop an efficient catalyst/reagent/solvent system for the synthesis of ureas or carboxylic acids. (2) To use in-situ spectroscopic and kinetic methods to study the mechanism of the synthesis of ureas or carboxylic acids. (3) To develop bifunctional ligands capable of secondary interactions with CO{sub 2}, to detect the interactions, and to demonstrate applications to catalysis.

Oxidase catalysis via aerobically generated hypervalent iodine intermediates

Science.gov (United States)

Maity, Asim; Hyun, Sung-Min; Powers, David C.

2018-02-01

The development of sustainable oxidation chemistry demands strategies to harness O2 as a terminal oxidant. Oxidase catalysis, in which O2 serves as a chemical oxidant without necessitating incorporation of oxygen into reaction products, would allow diverse substrate functionalization chemistry to be coupled to O2 reduction. Direct O2 utilization suffers from intrinsic challenges imposed by the triplet ground state of O2 and the disparate electron inventories of four-electron O2 reduction and two-electron substrate oxidation. Here, we generate hypervalent iodine reagents—a broadly useful class of selective two-electron oxidants—from O2. This is achieved by intercepting reactive intermediates of aldehyde autoxidation to aerobically generate hypervalent iodine reagents for a broad array of substrate oxidation reactions. The use of aryl iodides as mediators of aerobic oxidation underpins an oxidase catalysis platform that couples substrate oxidation directly to O2 reduction. We anticipate that aerobically generated hypervalent iodine reagents will expand the scope of aerobic oxidation chemistry in chemical synthesis.

Alkylation of hydrothiophosphoryl compounds in conditions of interphase catalysis

International Nuclear Information System (INIS)

Aladzheva, I.M.; Odinets, I.L.; Petrovskij, P.V.; Mastryukova, T.A.; Kabachkin, M.I.

1993-01-01

A method of interphase catalysis permitted to develop a common method for synthesis of compounds with thiophosphoryl group. The effect of nature of hydrothiophosphoryl compound, alkylating agent, two-phase system and reaction conditions on alkylation product yields was investigated in detail

2013 Gordon Research Conference, Inorganic reaction mechanisms, Galveston, TX, March 3-8 2013

Energy Technology Data Exchange (ETDEWEB)

Abu-Omar, Mahdi M. [Purdue Univ., West Lafayette, IN (United States)

2012-12-08

The 2013 Gordon Conference on Inorganic Reaction Mechanisms will present cutting-edge research on the molecular aspects of inorganic reactions involving elements from throughout the periodic table and state-of-the art techniques that are used in the elucidation of reaction mechanisms. The Conference will feature a wide range of topics, such as homogeneous and heterogeneous catalysis, metallobiochemistry, electron-transfer in energy reactions, polymerization, nitrogen fixation, green chemistry, oxidation, solar conversion, alkane functionalization, organotransition metal chemistry, and computational chemistry. The talks will cover themes of current interest including energy, materials, and bioinorganic chemistry. Sections cover: Electron-Transfer in Energy Reactions; Catalytic Polymerization and Oxidation Chemistry; Kinetics and Spectroscopy of Heterogeneous Catalysts; Metal-Organic Chemistry and its Application in Synthesis; Green Energy Conversion;Organometallic Chemistry and Activation of Small Molecules; Advances in Kinetics Modeling and Green Chemistry; Metals in Biology and Disease; Frontiers in Catalytic Bond Activation and Cleavage.

Reaction mechanisms in zeolite catalysis

NARCIS (Netherlands)

Rozanska, X.; Santen, van R.A.; Auerbach, S.C.; Carrado, K.A.; Dutta, P.D.

2003-01-01

A review; described are the most basic mechanistic reaction steps that are induced by zeolite catalysts. Details on the zeolitic properties that are relevant to mol. reactivity are also provided. The theor. methods and models at hand to allow the investigation of these reaction steps and that have

Erbium Salts as Non-Toxic Catalysts Compatible with Alternative Reaction Media

Directory of Open Access Journals (Sweden)

Manuela Oliverio

2018-03-01

Full Text Available Green catalysts must be non-toxic, easy to manage, able to be recovered and reused, active under alternative reaction conditions and cheap. Erbium salts meet all the previously listed characteristics and today they are emerging as a valuable catalytic solution to a number of organic transformations needing a Lewis acid catalyst in wet conditions or under alternative heating sources. This review aims to summarize the application of erbium salts in green organic transformations, with particular emphasis on their versatility under both homogeneous and heterogeneous conditions. The erbium salts’ role in bifunctional catalysis is also presented.

Sequential rhodium/palladium catalysis: enantioselective formation of dihydroquinolinones in the presence of achiral and chiral ligands.

Science.gov (United States)

Zhang, Lei; Qureshi, Zafar; Sonaglia, Lorenzo; Lautens, Mark

2014-12-08

Compatible combinations of achiral and chiral ligands can be used in rhodium/palladium catalysis to achieve highly enantioselective domino reactions. The difference in rates of catalysis and minimal effects of ligand interference confer control in the domino sequence. The "all-in-one" 1,4-conjugate arylation and C-N cross-coupling through sequential Rh/Pd catalysis provides access to enantioenriched dihydroquinolinone building blocks. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanostructured Membranes for Green Synthesis of Nanoparticles and Enzyme Catalysis

Science.gov (United States)

Macroporous membranes functionalized with ionizable macromolecules provide promising applications in toxic metal capture at high capacity, nanoparticle synthesis, and catalysis. Our low‐pressure membrane approach is marked by reaction and separation selectivity and their tunabili...

Nanostructured Membranes for Enzyme Catalysis and Green Synthesis of Nanoparticles

Science.gov (United States)

Macroporous membranes functionalized with ionizable macromolecules provide promising applications in toxic metal capture at high capacity, nanoparticle synthesis, and catalysis. Our low-pressure membrane approach is marked by reaction and separation selectivity and their tunabil...

Calculation of homogenized Pickering NGS stainless steel adjuster rod neutron cross-sections using conservation of reaction rates

Energy Technology Data Exchange (ETDEWEB)

Robinson, R C [Atlantic Nuclear Services Ltd. (Canada); Tran, F [Ontario Hydro, Pickering, ON (Canada). Pickering Generating Station

1996-12-31

A homogenization methodology for calculation of reactivity device incremental cross-sections has been developed using reaction rate conservation (RRC). A heterogeneous transport calculation of flux was utilised to produce the homogenized cross-sections for a finite difference two group diffusion code. The RRC cross-sections have been shown to improve significantly the prediction of reactivity worth for stainless steel adjuster rods installed in Pickering NGS reactors. (author). 10 refs., 3 tabs., 6 figs.

Surface science and heterogeneous catalysis

International Nuclear Information System (INIS)

Somorjai, G.A.

1980-05-01

The catalytic reactions studied include hydrocarbon conversion over platinum, the transition metal-catalyzed hydrogenation of carbon monoxide, and the photocatalyzed dissociation of water over oxide surfaces. The method of combined surface science and catalytic studies is similar to those used in synthetic organic chemistry. The single-crystal models for the working catalyst are compared with real catalysts by comparing the rates of cyclopropane ring opening on platinum and the hydrogenation of carbon monoxide on rhodium single crystal surface with those on practical commercial catalyst systems. Excellent agreement was obtained for these reactions. This document reviews what was learned about heterogeneous catalysis from these surface science approaches over the past 15 years and present models of the active catalyst surface

Asymmetric catalysis in the cyclopropanation of olefins; Catalise assimetrica na ciclopropanacao de olefinas

Energy Technology Data Exchange (ETDEWEB)

Leao, Raquel A.C.; Ferreira, Vitor F.; Pinheiro, Sergio [Universidade Federal Fluminense (UFF), Niteroi, RJ (Brazil). Dept. de Quimica Organica]. E-mail: cegvito@vm.uff.br

2007-07-01

The main methodologies in the asymmetric cyclopropanation of alkenes with emphasis on asymmetric catalysis are covered. Examples are the Simmons-Smith reaction, the use of diazoalkanes and reactions carried out by decomposition of alpha-diazoesters in the presence of transition metals. (author)

Catalysis of Nuclear Reactions by Electrons

Science.gov (United States)

Lipoglavšek, Matej

2018-01-01

Electron screening enhances nuclear reaction cross sections at low energies. We studied the nuclear reaction 1H(19F,αγ)16O in inverse kinematics in different solid hydrogen targets. Measured resonance strengths differed by up to a factor of 10 in different targets. We also studied the 2H(p,γ)3He fusion reaction and observed electrons emitted as reaction products instead of γ rays. In this case electron screening greatly enhances internal conversion probability.

Acid-base catalysis of N-[(morpholine)methylene]daunorubicin.

Science.gov (United States)

Krause, Anna; Jelińska, Anna; Cielecka-Piontek, Judyta; Klawitter, Maria; Zalewski, Przemysław; Oszczapowicz, Irena; Wąsowska, Małgorzata

2012-08-01

The stability of N-[(morpholine)methylene]-daunorubicin hydrochloride (MMD) was investigated in the pH range 0.44-13.54, at 313, 308, 303 and 298 K. The degradation of MMD as a result of hydrolysis is a pseudo-first-order reaction described by the following equation: ln c = ln c(0) - k(obs)• t. In the solutions of hydrochloric acid, sodium hydroxide, borate, acetate and phosphate buffers, k(obs) = k(pH) because general acid-base catalysis was not observed. Specific acid-base catalysis of MMD comprises the following reactions: hydrolysis of the protonated molecules of MMD catalyzed by hydrogen ions (k(1)) and spontaneous hydrolysis of MMD molecules other than the protonated ones (k(2)) under the influence of water. The total rate of the reaction is equal to the sum of partial reactions: k(pH) = k(1) • a(H)+ • f(1) + k(2) • f(2) where: k(1) is the second-order rate constant (mol(-1) l s(-1)) of the specific hydrogen ion-catalyzed degradation of the protonated molecules of MMD; k(2) is the pseudo-first-order rate constant (s(-1)) of the water-catalyzed degradation of MMD molecules other than the protonated ones, f(1) - f(2) are fractions of the compound. MMD is the most stable at approx. pH 2.5.

Extremely efficient catalysis of carbon-carbon bond formation using "click" dendrimer-stabilized palladium nanoparticles.

Science.gov (United States)

Astruc, Didier; Ornelas, Cátia; Diallo, Abdou K; Ruiz, Jaime

2010-07-20

This article is an account of the work carried out in the authors' laboratory illustrating the usefulness of dendrimer design for nanoparticle palladium catalysis. The "click" synthesis of dendrimers constructed generation by generation by 1-->3 C connectivity, introduces 1,2,3-triazolyl ligands insides the dendrimers at each generation. Complexation of the ligands by Pd(II) followed by reduction to Pd(0) forms dendrimer-stabilized Pd nanoparticles (PdNPs) that are extremely reactive in the catalysis of olefin hydrogenation and C-C bond coupling reactions. The stabilization can be outer-dendritic for the small zeroth-generation dendrimer or intra-dendritic for the larger first- and second-generation dendrimers. The example of the Miyaura-Suzuki reaction that can be catalyzed by down to 1 ppm of PdNPs with a "homeopathic" mechanism (the less, the better) is illustrated here, including catalysis in aqueous solvents.

Interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials: A review.

Science.gov (United States)

He, Jie; Yang, Xiaofang; Men, Bin; Wang, Dongsheng

2016-01-01

The heterogeneous Fenton reaction can generate highly reactive hydroxyl radicals (OH) from reactions between recyclable solid catalysts and H2O2 at acidic or even circumneutral pH. Hence, it can effectively oxidize refractory organics in water or soils and has become a promising environmentally friendly treatment technology. Due to the complex reaction system, the mechanism behind heterogeneous Fenton reactions remains unresolved but fascinating, and is crucial for understanding Fenton chemistry and the development and application of efficient heterogeneous Fenton technologies. Iron-based materials usually possess high catalytic activity, low cost, negligible toxicity and easy recovery, and are a superior type of heterogeneous Fenton catalysts. Therefore, this article reviews the fundamental but important interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials. OH, hydroperoxyl radicals/superoxide anions (HO2/O2(-)) and high-valent iron are the three main types of reactive oxygen species (ROS), with different oxidation reactivity and selectivity. Based on the mechanisms of ROS generation, the interfacial mechanisms of heterogeneous Fenton systems can be classified as the homogeneous Fenton mechanism induced by surface-leached iron, the heterogeneous catalysis mechanism, and the heterogeneous reaction-induced homogeneous mechanism. Different heterogeneous Fenton systems catalyzed by characteristic iron-based materials are comprehensively reviewed. Finally, related future research directions are also suggested. Copyright © 2015. Published by Elsevier B.V.

Crown ethers and phase transfer catalysis in polymer science

CERN Document Server

Carraher, Charles

1984-01-01

Phase transfer catalysis or interfacial catalysis is a syn­ thetic technique involving transport of an organic or inorganic salt from a solid or aqueous phase into an organic liquid where reaction with an organic-soluble substrate takes place. Over the past 15 years there has been an enormous amount of effort invested in the development of this technique in organic synthe­ sis. Several books and numerous review articles have appeared summarizing applications in which low molecular weight catalysts are employed. These generally include either crown ethers or onium salts of various kinds. While the term phase transfer catalysis is relatively new, the concept of using a phasetrans­ fer agent (PTA) is much older~ Both Schnell and Morgan employed such catalysts in synthesis of polymeric species in the early 1950's. Present developments are really extensions of these early applications. It has only been within the last several years that the use of phase transfer processes have been employed in polymer synthesis...

Catalysis-enhanced strengthening of porous materials

International Nuclear Information System (INIS)

Sokolova, L.N.; Shchukin, E.D.; Burenkova, L.N.; Romanovskij, B.V.

2000-01-01

Change in the strength of compressed tablets of the catalyst on the basis of ZrO 2 (84 mass %) and Y 2 O 3 (16 mass %) after conducting the endothermal reaction of the methanol and ethanol dehydration at 700-800 deg C is studied. It is shown, that the key factor, determining the strengthening effect by 65-88% is not at all the reaction exothermal nature, which could lead to local heating of the catalyst surface. In reality significant increase in concentration of surface defects, as compared to the equilibrium at the given temperature is achieved on the account of conjugation of processes of catalysis and surface defects formation [ru

Production of Biodiesel from Shea Butter Oil using Homogeneous Catalysts

Directory of Open Access Journals (Sweden)

Jude EJEH

2014-02-01

Full Text Available An investigation into the production of biodiesel from shea butter oil using homogenous catalyst was carried out. The properties of the oil obtained were first determined, having an FFA value of 2.279 amongst other properties. Thus, the direct base-catalysis method was used, with potassium hydroxide as the catalyst. In a 1 hour batch run, biodiesel was produced with a conversion of 92%, FAME content of 97.1%, cetane number of 46.84 and kinematic viscosity of 4.30mm2/s, conforming to ASTM D6751 and EN 14214 international standards. As such, it was established that shea butter biodiesel could be produced by the direct base catalysis, over a shorter time with low cost chemicals.

Confined catalysis under two-dimensional materials

OpenAIRE

Li, Haobo; Xiao, Jianping; Fu, Qiang; Bao, Xinhe

2017-01-01

Small spaces in nanoreactors may have big implications in chemistry, because the chemical nature of molecules and reactions within the nanospaces can be changed significantly due to the nanoconfinement effect. Two-dimensional (2D) nanoreactor formed under 2D materials can provide a well-defined model system to explore the confined catalysis. We demonstrate a general tendency for weakened surface adsorption under the confinement of graphene overlayer, illustrating the feasible modulation of su...

Exploring the Cattaneo-Christov heat flux phenomenon on a Maxwell-type nanofluid coexisting with homogeneous/heterogeneous reactions

Science.gov (United States)

Sarkar, Amit; Kundu, Prabir Kumar

2017-12-01

This specific article unfolds the efficacy of Cattaneo-Christov heat flux on the heat and mass transport of Maxwell nanofluid flow over a stretched sheet with changeable thickness. Homogeneous/heterogeneous reactions in the fluid are additionally considered. The Cattaneo-Christov heat flux model is initiated in the energy equation. Appropriate similarity transformations are taken up to form a system of nonlinear ODEs. The impact of related parameters on the nanoparticle concentration and temperature is inspected through tables and diagrams. It is renowned that temperature distribution increases for lower values of the thermal relaxation parameter. The rate of mass transfer is enhanced for increasing in the heterogeneous reaction parameter but the reverse tendency is ensued for the homogeneous reaction parameter. On the other side, the rate of heat transfer is getting enhanced for the Cattaneo-Christov model compared to the classical Fourier's model for some flow factors. Thus the implication of the current study is to delve its unique effort towards the generalized version of traditional Fourier's law at nano level.

Heterogeneous Catalysis of Polyoxometalate Based Organic–Inorganic Hybrids

Directory of Open Access Journals (Sweden)

Yuanhang Ren

2015-03-01

Full Text Available Organic–inorganic hybrid polyoxometalate (POM compounds are a subset of materials with unique structures and physical/chemical properties. The combination of metal-organic coordination complexes with classical POMs not only provides a powerful way to gain multifarious new compounds but also affords a new method to modify and functionalize POMs. In parallel with the many reports on the synthesis and structure of new hybrid POM compounds, the application of these compounds for heterogeneous catalysis has also attracted considerable attention. The hybrid POM compounds show noteworthy catalytic performance in acid, oxidation, and even in asymmetric catalytic reactions. This review summarizes the design and synthesis of organic–inorganic hybrid POM compounds and particularly highlights their recent progress in heterogeneous catalysis.

Advances in interactive supported electro-catalysis for hydrogen and oxygen electrode reactions

Energy Technology Data Exchange (ETDEWEB)

Nedeljko V Krstajic; Ljiljana M Vracar; Jelena M Jaksic; Milan M Jaksic [Faculty of Technology and Metallurgy, University of Belgrade, Belgrade, Serbia and Montenegro (Yugoslavia); Stelios G Neophytides; Miranda Labou; Jelena M Jaksic; Milan M Jaksic [Institute of Chemical Engineering and High Temperature Chemical Processes FORTH, and Department of Chemistry, University of Patras, 26500 Patras, (Greece); Reidar Tunold [University of Trondheim, NTNU, Institute of Industrial Electrochemistry, Trondheim, (Norway); Polycarpos Falaras [Institute of Physical Chemistry, NCSR Demokritos, Attikis, Athens, (Greece)

2006-07-01

Magneli phases have been introduced as an unique electron conductive and interactive support for electro-catalysis both in hydrogen (HELR) and oxygen (OELR) electrode reactions in water electrolysis and Low Temperature PEM Fuel Cells (LT PEM FC). The Strong Metal-Support Interaction (SMSI) that imposes the former implies: (i) the hypo-hyper-d inter-bonding effect and its catalytic consequences, and (ii) the interactive primary oxide (M-OH) spillover from the hypo-d-oxide support as a dynamic electrocatalytic contribution. The stronger the bonding, the more strained appear d-orbitals, thereby the less strong the intermediate adsorptive strength in the rate determining step (RDS), and consequently, the faster the facilitated catalytic electrode reaction arises. At the same time the primary oxide spillover transferred from the hypo-d-oxide support directly interferes and reacts either individually and directly to contribute to finish the oxygen reduction, or with other interactive species, like CO to contribute to the CO tolerance. In such a respect, the conditions to provide Au to act as the reversible hydrogen electrode have been proved either by its potentiodynamic surface reconstruction in a heavy water solution, or by the nano-structured SMSI Au on anatase titania with characteristic strained d-orbitals in such a hypo-hyper-d-interactive bonding (Au/TiO{sub 2}). In the same context, the monoatomic network dispersion of Pt upon Magneli phases makes it possible to produce an advanced interactive supported electro-catalyst for cathodic oxygen reduction (ORR). The strained hypo-hyper-d-inter-electronic and inter-d-orbital metal/hypo-d-oxide support bonding relative to the strength of the latter, has been inferred to be the basis of the synergistic electrocatalytic effect both in the HELR and ORR. (authors)

Defect-induced Catalysis toward the Oxygen Reduction Reaction in Single-walled Carbon Nanotube: Nitrogen doped and Non-nitrogen doped

International Nuclear Information System (INIS)

Lu, Di; Wu, Dan; Jin, Jian; Chen, Liwei

2016-01-01

Single-walled carbon nanotubes (SWNTs) are post-treated by argon (Ar) or ammonia (NH 3 ) plasma irradiation to introduce defects that are potentially related to catalysis towards the oxygen reduction reaction (ORR). Electrochemical characterization in alkali medium suggests that the plasma irradiated SWNTs demonstrate enhanced catalytic activity toward the ORR with a positively shifted threshold potential. Moreover the enhanced desired four-electron pathway catalytic activity, which exhibited as the positive shifted threshold potential, is independent of the nitrogen dopant. The nature of the defects is probed with Raman and X-ray photoelectron spectroscopy. The results indicate that the non-nitrogen doped defects of SWNTs contribute to the actual active site for the ORR.

In situ NMR studies of reactions on catalysts

Energy Technology Data Exchange (ETDEWEB)

Haw, James F [Texas A and M Univ., College Station, TX (United States). Dept. of Chemistry

1994-12-31

Zeolites are useful in the synthesis of fine chemicals. The systematic understanding of organic chemistry of zeolite catalysis may contribute to: the elucidation of reaction mechanisms of existing catalytic processes; the discovery of new catalytic reactions; the application of zeolite catalysis to the synthesis of fine chemicals. This work presents species of zeolites identified by in situ NMR; reactions of organic chemicals on zeolites and proposes mechanisms as well as reactivity trends 3 refs., 7 tabs.

Two-dimensional zeolites in catalysis: current status and perspectives

Czech Academy of Sciences Publication Activity Database

Opanasenko, Maksym; Roth, Wieslaw Jerzy; Čejka, Jiří

2016-01-01

Roč. 6, č. 8 (2016), s. 2467-2484 ISSN 2044-4753 R&D Projects: GA ČR GP13-17593P; GA ČR(CZ) GAP106/12/0189 Institutional support: RVO:61388955 Keywords : mesoporous molecular sieves * catalysis * acylation reactions Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.773, year: 2016

Horizons in catalysis

Energy Technology Data Exchange (ETDEWEB)

Idol, J D

1979-04-21

A discussion covers a brief historical review of industrial catalysis; a survey of major present-day catalytic processes in the petroleum and petrochemical industries; the outlook for the industrial catalyst applications in coal liquefaction, conversion of coal liquids, shale oil, and other synthetic crude sources for transportation fuels, and synthesis gas-based processes; some important directions for future developments, including phase transfer catalysis, photocatalysis, and advanced techniques for catalyst studies; and the need for closer industry-university and industry-government cooperation in the field of catalysis.

Regulating the surface of nanoceria and its applications in heterogeneous catalysis

Science.gov (United States)

Ma, Yuanyuan; Gao, Wei; Zhang, Zhiyun; Zhang, Sai; Tian, Zhimin; Liu, Yuxuan; Ho, Johnny C.; Qu, Yongquan

2018-03-01

Ceria (CeO2) as a support, additive, and active component for heterogeneous catalysis has been demonstrated to have great catalytic performance, which includes excellent thermal structural stability, catalytic efficiency, and chemoselectivity. Understanding the surface properties of CeO2 and the chemical reactions occurred on the corresponding interfaces is of great importance in the rational design of heterogeneous catalysts for various reactions. In general, the reversible Ce3+/Ce4+ redox pair and the surface acid-base properties contribute to the superior intrinsic catalytic capability of CeO2, and hence yield enhanced catalytic phenomenon in many reactions. Particularly, nanostructured CeO2 is characterized by a large number of surface-bound defects, which are primarily oxygen vacancies, as the surface active catalytic sites. Many efforts have therefore been made to control the surface defects and properties of CeO2 by various synthetic strategies and post-treatments. The present review provides a comprehensive overview of recent progress in regulating the surface structure and composition of CeO2 and its applications in catalysis.

Understanding of catalysis on early transition metal oxide-based catalysts through exploration of surface structure and chemistry during catalysis using in-situ approaches

Energy Technology Data Exchange (ETDEWEB)

Tao, Franklin [Univ. of Kansas, Lawrence, KS (United States). Dept. of Chemical and Petroleum Engineering. Dept. of Chemistry

2015-09-14

Two main categories of heterogeneous catalysts are metal and metal oxide which catalyze 80% chemical reactions at solid-gas and solid-liquid interfaces. Metal oxide catalysts are much more complicated than metal catalysts. The reason is that the cations of the metal atoms could exhibit a few different oxidation states on surface of the same catalyst particle such as Co₃O₄ or change of their oxidation states under different reactive environments. For a metal catalyst, there is only one oxidation state typically. In addition, surface of a metal oxide can be terminated with multiple surface functionalities including O atoms with different binding configurations and OH group. For metal, only metal atoms are exposed typically. Obviously, the complication of surface chemistry and structure of a metal oxide makes studies of surface of an oxide catalyst very challenging. Due to the complication of surface of a meal oxide, the electronic and geometric structures of surface of a metal oxide and the exposed species have received enormous attention since oxide catalysts catalyze at least 1/3 chemical reactions in chemical and energy industries. Understanding of catalytic reactions on early transition metal oxide-based catalysts is fundamentally intriguing and of great practical interest in energy- and environment-related catalysis. Exploration of surface chemistry of oxide-based catalysts at molecular level during catalysis has remained challenging though it is critical in deeply understanding catalysis on oxide-based catalysts and developing oxide-based catalysts with high activity and selectivity. Thus, the overall objective of this project is to explore surface chemistry and structure of early transition metal oxide-based catalysts through in-situ characterization of surface of catalysts, measurements of catalytic performances, and then build an intrinsic correlation of surface chemistry and structure with their catalytic performances in a few

Dynamic Self-Assembly of Homogenous Microcyclic Structures Controlled by a Silver-Coated Nanopore.

Science.gov (United States)

Gao, Rui; Lin, Yao; Ying, Yi-Lun; Liu, Xiao-Yuan; Shi, Xin; Hu, Yong-Xu; Long, Yi-Tao; Tian, He

2017-07-01

The self-assembly of nanoparticles is a challenging process for organizing precise structures with complicated and ingenious structures. In the past decades, a simple, high-efficiency, and reproducible self-assembly method from nanoscale to microscale has been pursued because of the promising and extensive application prospects in bioanalysis, catalysis, photonics, and energy storage. However, microscale self-assembly still faces big challenges including improving the stability and homogeneity as well as pursuing new assembly methods and templates for the uniform self-assembly. To address these obstacles, here, a novel silver-coated nanopore is developed which serves as a template for electrochemically generating microcyclic structures of gold nanoparticles at micrometers with highly homogenous size and remarkable reproducibility. Nanopore-induced microcyclic structures are further applied to visualize the diffusion profile of ionic flux. Based on this novel strategy, a nanopore could potentially facilitate the delivery of assembled structures for many practical applications including drug delivery, cellular detection, catalysis, and plasmonic sensing. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermodynamics of coproportionation reactions of homogeneous samarium (3) and yttrium (3) nitrates solvates with neutral organic phosphorus compounds

International Nuclear Information System (INIS)

Pyartman, A.K.

1995-01-01

Reaction heats of homogeneous samarium (3) and yttrium (3) nitrate solvates coproportionation with neutral organophosphoric compounds (tri-n.-butylphosphate, diisooctylmethylphosphonate, diisoamylmethylphosphonate) at T=298.15 K in hexane have been measured by thermochemical method. It has been ascertained that enthalpies of coproportionation reactions practically do not depend on the nature, concentration of rare earth metal (3) nitrate solvates in hexane, nature of neutral organophosphoric compound and constitute 1.1±-.2 kJ/mol. The Gibbs free energy of coproportionation reactions is -5.43 kJ/mol, while entropy of the reactions in 14.5±0.7 J/mol·K. 8 refs., 1 tab

Kinetic Isotope Effects (KIE) and Density Functional Theory (DFT): A Match Made in Heaven?

DEFF Research Database (Denmark)

Christensen, Niels Johan; Fristrup, Peter

2015-01-01

Determination of experimental kinetic isotope effects (KIE) is one of the most useful tools for the exploration of reaction mechanisms in organometallic chemistry. The approach has been further strengthened during the last decade with advances in modern computational chemistry. This allows for th...... reaction). The approach is highlighted by using recent examples from both stoichiometric and catalytic reactions, homogeneous and heterogeneous catalysis, and enzyme catalysis to illustrate the expected accuracy and utility of this approach....

Intramolecular and Transannular Diels-Alder Reactions

DEFF Research Database (Denmark)

Tanner, David Ackland; Ascic, Erhad

2014-01-01

Few reactions can compete with the Diels-Alder (DA) [4+2] cycloaddition for the rapid and efficient generation of molecular complexity. The DA reaction is atom-economic and stereospecific, as well as diastereo- and regioselective. The intramolecular version (IMDA) of the DA cycloaddition and its...... and dienophile, methods for acceleration of IMDA reactions (such as use of high pressure) and catalysis (using oxophilic or carbophilic metal complexes, Brønsted acids, and enzymes). The use of furans as diene components (IMDAF), intramolecular hetero-DA (IMHDA) and IMDA reactions with inverse electron demand...... are also covered. Applications of IMDA to asymmetric synthesis (from substrate control through to enantioselective catalysis, including organocatalysis) are presented, along with tandem sequences involving IMDA cycloaddition. A theme pervading the whole chapter is the use of IMDA reactions for the total...

Numerical study for Darcy-Forchheimer flow due to a curved stretching surface with Cattaneo-Christov heat flux and homogeneous-heterogeneous reactions

Directory of Open Access Journals (Sweden)

Tasawar Hayat

Full Text Available The current investigation presents Darcy-Forchheimer flow of viscous fluid caused by a curved stretching sheet. Flow for porous space is characterized by Darcy-Forchheimer relation. Concept of homogeneous and heterogeneous reactions is also utilized. Heat transfer for Cattaneo–Christov theory characterizing the feature of thermal relaxation is incorporated. Nonlinear differential systems are derived. Shooting algorithm is employed to construct the solutions for the resulting nonlinear system. The characteristics of various sundry parameters are studied and discussed. Skin friction coefficient and heat transfer rate are numerically described. Keywords: 2D flow, Curved stretching surface, Darcy-Forchheimer porous medium, Cattaneo-Christov heat flux, Homogeneous-heterogeneous reactions

Chemical Reactions Catalyzed by Metalloporphyrin-Based Metal-Organic Frameworks

Directory of Open Access Journals (Sweden)

Kelly Aparecida Dias de Freitas Castro

2013-06-01

Full Text Available The synthetic versatility and the potential application of metalloporphyrins (MP in different fields have aroused researchers’ interest in studying these complexes, in an attempt to mimic biological systems such as cytochrome P-450. Over the last 40 years, synthetic MPs have been mainly used as catalysts for homogeneous or heterogeneous chemical reactions. To employ them in heterogeneous catalysis, chemists have prepared new MP-based solids by immobilizing MP onto rigid inorganic supports, a strategy that affords hybrid inorganic-organic materials. More recently, materials obtained by supramolecular assembly processes and containing MPs as building blocks have been applied in a variety of areas, like gas storage, photonic devices, separation, molecular sensing, magnets, and heterogeneous catalysis, among others. These coordination polymers, known as metal-organic frameworks (MOFs, contain organic ligands or complexes connected by metal ions or clusters, which give rise to a 1-, 2- or 3-D network. These kinds of materials presents large surface areas, Brønsted or redox sites, and high porosity, all of which are desirable features in catalysts with potential use in heterogeneous phases. Building MOFs based on MP is a good way to obtain solid catalysts that offer the advantages of bioinspired systems and zeolitic materials. In this mini review, we will adopt a historical approach to present the most relevant MP-based MOFs applicable to catalytic reactions such as oxidation, reduction, insertion of functional groups, and exchange of organic functions.

Applications of functionalized polymers in catalysis. Progress report 3, July 15, 1979-July 1, 1980

Energy Technology Data Exchange (ETDEWEB)

Bergbreiter, D.E.

1980-07-01

Research on applications of polymers in catalysis has encompassed three areas: the use of functionalized polymers to detect soluble intermediates in heterogeneous Group VIII metal catalyzed arene hydrogenations; a study of olefin isomerization and hydrogenations catalyzed by polystyrene supported bis(cyclopentadienyl)titanium dichloride and an alkylmagnesium halide; and the acceleration in rate of an olefin hydrogenation catalyzed by homogeneous rhodium and ruthenium complexes as a result of absorption of triphenylphosphine by silver (I) polystyrenesulfonate. The first project found that polymer bound trapping agents were unable to detect soluble intermediates such as dienes, free radicals, or reducing agents in platinum-catalyzed benzene hydrogenation at 60 psi H/sub 2/ and 30/sup 0/C. The inability to detect diene intermediates was shown to be the result of the lower reactivity of the polymeric reagent versus an active catalyst. The polymer-supported titanium catalysts studied were unusual in that immobilization of a catalyst in this case altered the catalyst's specificity relative to its homogeneous counterpart. Preliminary results from the third project demonstrate the potential of simple functionalized polymers to improve existing homogeneously catalyzed reactions. Rate increases for olefin hydrogenations using C1Rh(Ph/sub 3/P)/sub 3/, HRh(CO)(Ph/sub 3/)/sub 3/, HRu(OAc)(Ph/sub 3/P), H/sub 2/Ru(Ph/sub 3/P)/sub 4/, Cl/sub 2/Ru(Ph/sub 3/P)/sub 3/, and Cl/sub 2/Ru(Ph/sub 3/P)/sub 4/ ranged from 25 to 3000%.

UV Catalysis, Cyanotype Photography, and Sunscreens

Science.gov (United States)

Lawrence, Glen D.; Fishelson, Stuart

1999-09-01

This laboratory experiment is intended for a chemistry course for non-science majors. The experiment utilizes one of the earliest photographic processes, the cyanotype process, to demonstrate UV catalysis of chemical reactions. In addition to making photographic prints from negatives, the process can be used to test the effectiveness of sunscreens and the relative efficacy of the SPF (sun protection factor) rating of sunscreens. This is an inexpensive process, requiring solutions of ammonium ferric citrate and potassium ferricyanide, with options to use hydrogen peroxide and ammonium hydroxide solutions. Students can prepare their own UV-sensitized paper with the indicated chemicals and watch the photographic image appear as it is exposed to sunlight or fluorescent UV lamps in a light box designed for use in this experiment. The laboratory experiment should stimulate discussion of UV catalysis, photographic processes and photochemistry, sunscreens, and UV damage to biological organisms. The chemicals used are relatively nontoxic, and the procedure is simple enough to be used by groups of diverse ages and abilities.

Deuterium labelling of tryptamine, serotonin and their N-methylated metabolites using solvent exchange reactions

Energy Technology Data Exchange (ETDEWEB)

Raeisaenen, M; Kaerkkaeinen, J [Helsinki Univ. (Finland). Dept. of Medical Chemistry

1979-01-01

Technically uncomplicated methods based on catalytic isotope exchange in deuterated solvents are described for the deuteration of tryptamine, serotonin and their N-methylated metabolites. Heterogeneous platinum catalysis, homogeneous acid catalysis and their combination have been employed. The properties of the labelled derivatives prepared with each technique as well as their use in mass spectrometric work are discussed.

Deuterium labelling of tryptamine, serotonin and their N-methylated metabolites using solvent exchange reactions

International Nuclear Information System (INIS)

Raeisaenen, M.; Kaerkkaeinen, J.

1979-01-01

Technically uncomplicated methods based on catalytic isotope exchange in deuterated solvents are described for the deuteration of tryptamine, serotonin and their N-methylated metabolites. Heterogeneous platinum catalysis, homogeneous acid catalysis and their combination have been employed. The properties of the labelled derivatives prepared with each technique as well as their use in mass spectrometric work are discussed. (author)

Predictive Modeling in Actinide Chemistry and Catalysis

Energy Technology Data Exchange (ETDEWEB)

Yang, Ping [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

2016-05-16

These are slides from a presentation on predictive modeling in actinide chemistry and catalysis. The following topics are covered in these slides: Structures, bonding, and reactivity (bonding can be quantified by optical probes and theory, and electronic structures and reaction mechanisms of actinide complexes); Magnetic resonance properties (transition metal catalysts with multi-nuclear centers, and NMR/EPR parameters); Moving to more complex systems (surface chemistry of nanomaterials, and interactions of ligands with nanoparticles); Path forward and conclusions.

Morphology-controlled synthesis of silver nanostructures via a seed catalysis process

Science.gov (United States)

Chen, Chang; Wang, Li; Yu, Haojie; Wang, Jianjun; Zhou, Junfeng; Tan, Qiaohua; Deng, Libo

2007-03-01

A novel, effective strategy named 'seed catalysis' has been described here to synthesize silver nanostructures with controllable morphology. Typically, we added Na2S into the reaction system and the Ag2S semiconductor colloids formed at the initial stage would act as both seeds and catalyst in the silver reduction. The morphology of products is controlled by the concentration of Na2S added to the system. Low concentration of Na2S gives nanocubes of 40-50 nm in size, while a high concentration of Na2S is of benefit to obtain nanowires. The growth of the silver crystal is also accelerated by the catalysis of Ag2S. Electron microscopy and UV-vis absorption spectra have been used to investigate the evolution of silver nanowires, and a reasonable mechanism to explain the role of Ag2S seeds has also been suggested. This semiconductor seed catalysis strategy will provide wide applications in the fabrication of metal nanomaterials.

Morphology-controlled synthesis of silver nanostructures via a seed catalysis process

International Nuclear Information System (INIS)

Chen Chang; Wang Li; Yu Haojie; Wang Jianjun; Zhou Junfeng; Tan Qiaohua; Deng Libo

2007-01-01

A novel, effective strategy named 'seed catalysis' has been described here to synthesize silver nanostructures with controllable morphology. Typically, we added Na 2 S into the reaction system and the Ag 2 S semiconductor colloids formed at the initial stage would act as both seeds and catalyst in the silver reduction. The morphology of products is controlled by the concentration of Na 2 S added to the system. Low concentration of Na 2 S gives nanocubes of 40-50 nm in size, while a high concentration of Na 2 S is of benefit to obtain nanowires. The growth of the silver crystal is also accelerated by the catalysis of Ag 2 S. Electron microscopy and UV-vis absorption spectra have been used to investigate the evolution of silver nanowires, and a reasonable mechanism to explain the role of Ag 2 S seeds has also been suggested. This semiconductor seed catalysis strategy will provide wide applications in the fabrication of metal nanomaterials

Process spectroscopy in microemulsions—Raman spectroscopy for online monitoring of a homogeneous hydroformylation process

International Nuclear Information System (INIS)

Paul, Andrea; Meyer, Klas; Ruiken, Jan-Paul; Maiwald, Michael; Illner, Markus; Müller, David-Nicolas; Esche, Erik; Wozny, Günther; Westad, Frank

2017-01-01

A major industrial reaction based on homogeneous catalysis is hydroformylation for the production of aldehydes from alkenes and syngas. Hydroformylation in microemulsions, which is currently under investigation at Technische Universität Berlin on a mini-plant scale, was identified as a cost efficient approach which also enhances product selectivity. Herein, we present the application of online Raman spectroscopy on the reaction of 1-dodecene to 1-tridecanal within a microemulsion. To achieve a good representation of the operation range in the mini-plant with regard to concentrations of the reactants a design of experiments was used. Based on initial Raman spectra partial least squares regression (PLSR) models were calibrated for the prediction of 1-dodecene and 1-tridecanal. Limits of predictions arise from nonlinear correlations between Raman intensity and mass fractions of compounds in the microemulsion system. Furthermore, the prediction power of PLSR models becomes limited due to unexpected by-product formation. Application of the lab-scale derived calibration spectra and PLSR models on online spectra from a mini-plant operation yielded promising estimations of 1-tridecanal and acceptable predictions of 1-dodecene mass fractions suggesting Raman spectroscopy as a suitable technique for process analytics in microemulsions. (paper)

Insights into Sonogashira cross-coupling by high-throughput kinetics and descriptor modeling

NARCIS (Netherlands)

an der Heiden, M.R.; Plenio, H.; Immel, S.; Burello, E.; Rothenberg, G.; Hoefsloot, H.C.J.

2008-01-01

A method is presented for the high-throughput monitoring of reaction kinetics in homogeneous catalysis, running up to 25 coupling reactions in a single reaction vessel. This method is demonstrated and validated on the Sonogashira reaction, analyzing the kinetics for almost 500 coupling reactions.

Catalysis with Gold Complexes Immobilised on Carbon Nanotubes by π-π Stacking Interactions: Heterogeneous Catalysis versus the Boomerang Effect.

Science.gov (United States)

Vriamont, Charles; Devillers, Michel; Riant, Olivier; Hermans, Sophie

2013-09-02

A new pyrene-tagged gold(I) complex has been synthesised and tested as a homogeneous catalyst. First, a simple 1,6-enyne was chosen as a model substrate for cyclisation by using different solvents to optimise the reaction conditions. The non-covalent immobilisation of our pyrene-tagged gold complex onto multi-walled carbon nanotubes through π-π stacking interactions was then explored to obtain a supported homogeneous catalyst. The heterogenised catalyst and its homogeneous counterpart exhibited similar activity in a range of enyne cyclisation reactions. Bearing in mind that π-π interactions are affected by temperature and solvent polarity, the reuse and robustness of the supported homogeneous catalyst was tested to explore the scope and limitations of the recyclability of this catalyst. Under the optimised conditions, recyclability was observed by using the concept of the boomerang effect. Copyright © 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.

Interrelation of chemistry and process design in biodiesel manufacturing by heterogeneous catalysis

NARCIS (Netherlands)

Dimian, A.C.; Srokol, Z.W.; Mittelmeijer-Hazeleger, M.C.; Rothenberg, G.

2010-01-01

The pros and cons of using heterogeneous catalysis for biodiesel manufacturing are introduced, and explained from a chemistry and engineering viewpoint. Transesterification reactions of various feed types are then compared in batch and continuous process operation modes. The results show that the

Catalysis by Dust Grains in the Solar Nebula

Science.gov (United States)

Kress, Monika E.; Tielens, Alexander G. G. M.

1996-01-01

In order to determine whether grain-catalyzed reactions played an important role in the chemistry of the solar nebula, we have applied our time-dependent model of methane formation via Fischer-Tropsch catalysis to pressures from 10(exp -5) to 1 bar and temperatures from 450 to 650 K. Under these physical conditions, the reaction 3H2 + CO yields CH4 + H2O is readily catalyzed by an iron or nickel surface, whereas the same reaction is kinetically inhibited in the gas phase. Our model results indicate that under certain nebular conditions, conversion of CO to methane could be extremely efficient in the presence of iron-nickel dust grains over timescales very short compared to the lifetime of the solar nebula.

Environmental catalysis

International Nuclear Information System (INIS)

Montes Consuelo; Villa, Aida Luz

1996-01-01

The term environmental catalysis has been used lately to refer to a variety of applications of the catalysis, those which, they have grouped in the following categories: a) Control of emissions (chimney Gases and gases of the vehicles, Compound Organic Volatile (VOC), Scents, Chlorofluorocarbons) b) Conversion of having undone solids or liquids. C) Selective obtaining of alternating products that replace polluting compounds. d)replacement of catalysis environmentally dangerous And e)Development of catalysts for the obtaining of valuable chemical products without the formation of polluting by-products. In the group of Environmental Catalysis comes working in the first category, Particularly, in the exploration of active catalysts in the decrease of the emissions coming from combustion systems, carbon monoxide, hydrocarbons, nitrogen oxides (NOx), N20 and sulfur (SOx). Our fundamental premise is that the molecular meshes are catalytic potential for the development of a technology environmentally clean. These materials understand a class of inorganic compound with unique properties and intimately related with the structure. The net of the molecular meshes consists on tetrahedral configuration atoms (Al,Si, P, etc.) united to each other by oxygen atoms. As a result they are not formed three-dimensional structures alone with channels and cavities but also, with openings bounded by rings that consist of a certain number of tetrahedral atoms

Numerical tackling for viscoelastic fluid flow in rotating frame considering homogeneous-heterogeneous reactions

Directory of Open Access Journals (Sweden)

Najwa Maqsood

Full Text Available This study provides a numerical treatment for rotating flow of viscoelastic (Maxwell fluid bounded by a linearly deforming elastic surface. Mass transfer analysis is carried out in the existence of homogeneous-heterogeneous reactions. By means of usual transformation, the governing equations are changed into global similarity equations which have been tackled by an expedient shooting approach. A contemporary numerical routine bvp4c of software MATLAB is also opted to develop numerical approximations. Both methods of solution are found in complete agreement in all the cases. Velocity and concentration profiles are computed and elucidated for certain range of viscoelastic fluid parameter. The solutions contain a rotation-strength parameter λ that has a considerable impact on the flow fields. For sufficiently large value of λ, the velocity fields are oscillatory decaying function of the non-dimensional vertical distance. Concentration distribution at the surface is found to decrease upon increasing the strengths of chemical reactions. A comparison of present computations is made with those of already published ones and such comparison appears convincing. Keywords: Maxwell fluid, Similarity solution, Numerical method, Chemical reaction, Stretching sheet

CO- and HCl-free synthesis of acid chlorides from unsaturated hydrocarbons via shuttle catalysis

Science.gov (United States)

Fang, Xianjie; Cacherat, Bastien; Morandi, Bill

2017-11-01

The synthesis of carboxylic acid derivatives from unsaturated hydrocarbons is an important process for the preparation of polymers, pharmaceuticals, cosmetics and agrochemicals. Despite its industrial relevance, the traditional Reppe-type carbonylation reaction using pressurized CO is of limited applicability to laboratory-scale synthesis because of: (1) the safety hazards associated with the use of CO, (2) the need for special equipment to handle pressurized gas, (3) the low reactivity of several relevant nucleophiles and (4) the necessity to employ different, often tailor-made, catalytic systems for each nucleophile. Herein we demonstrate that a shuttle-catalysis approach enables a CO- and HCl-free transfer process between an inexpensive reagent, butyryl chloride, and a wide range of unsaturated substrates to access the corresponding acid chlorides in good yields. This new transformation provides access to a broad range of carbonyl-containing products through the in situ transformation of the reactive acid chloride intermediate. In a broader context, this work demonstrates that isodesmic shuttle-catalysis reactions can unlock elusive catalytic reactions.

Molecular-Level Design of Heterogeneous Chiral Catalysis

International Nuclear Information System (INIS)

Zaera, Francisco

2012-01-01

The following is a proposal to continue our multi-institutional research on heterogeneous chiral catalysis. Our team combines the use of surface-sensitive analytical techniques for the characterization of model systems with quantum and statistical mechanical calculations to interpret experimental data and guide the design of future research. Our investigation focuses on the interrelation among the three main mechanisms by which enantioselectivity can be bestowed to heterogeneous catalysts, namely: (1) by templating chirality via the adsorption of chiral supramolecular assemblies, (2) by using chiral modifiers capable of forming chiral complexes with the reactant and force enantioselective surface reactions, and (3) by forming naturally chiral surfaces using imprinting chiral agents. Individually, the members of our team are leaders in these various aspects of chiral catalysis, but the present program provides the vehicle to generate and exploit the synergies necessary to address the problem in a comprehensive manner. Our initial work has advanced the methodology needed for these studies, including an enantioselective titration procedure to identify surface chiral sites, infrared spectroscopy in situ at the interface between gases or liquids and solids to mimic realistic catalytic conditions, and DFT and Monte Carlo algorithms to simulate and understand chirality on surfaces. The next step, to be funded by the monies requested in this proposal, is to apply those methods to specific problems in chiral catalysis, including the identification of the requirements for the formation of supramolecular surface structures with enantioselective behavior, the search for better molecules to probe the chiral nature of the modified surfaces, the exploration of the transition from supramolecular to one-to-one chiral modification, the correlation of the adsorption characteristics of one-to-one chiral modifiers with their physical properties, in particular with their configuration

Synthesis of propylene carbonate from urea and propylene glycol over zinc oxide: A homogeneous reaction

Directory of Open Access Journals (Sweden)

Dengfeng Wang

2014-11-01

Full Text Available In this work, several metal oxides and zinc salts were used to catalyze propylene carbonate (PC synthesis from urea and propylene glycol (PG. According to the results of catalytic test and characterization, the catalytic pattern of ZnO was different from that of other metal oxides such as CaO, MgO and La2O3, but similar to that of zinc salts. In fact, the leaching of Zn species took place during reaction for ZnO. And ZnO was found to be the precursor of homogenous catalyst for reaction of urea and PG. Thus, the relationship between the amount of dissolved zinc species and the catalytic performance of employed ZnO was revealed. In addition, a possible reaction mechanism over ZnO was discussed based on the catalytic runs and the characterization of XRD, FTIR, and element analysis.

Hydrogen Tunneling Links Protein Dynamics to Enzyme Catalysis

Science.gov (United States)

Klinman, Judith P.; Kohen, Amnon

2014-01-01

The relationship between protein dynamics and function is a subject of considerable contemporary interest. Although protein motions are frequently observed during ligand binding and release steps, the contribution of protein motions to the catalysis of bond making/breaking processes is more difficult to probe and verify. Here, we show how the quantum mechanical hydrogen tunneling associated with enzymatic C–H bond cleavage provides a unique window into the necessity of protein dynamics for achieving optimal catalysis. Experimental findings support a hierarchy of thermodynamically equilibrated motions that control the H-donor and -acceptor distance and active-site electrostatics, creating an ensemble of conformations suitable for H-tunneling. A possible extension of this view to methyl transfer and other catalyzed reactions is also presented. The impact of understanding these dynamics on the conceptual framework for enzyme activity, inhibitor/drug design, and biomimetic catalyst design is likely to be substantial. PMID:23746260

Homogeneous versus heterogeneous zeolite nucleation

NARCIS (Netherlands)

Dokter, W.H.; Garderen, van H.F.; Beelen, T.P.M.; Santen, van R.A.; Bras, W.

1995-01-01

Aggregates of fractal dimension were found in the intermediate gel phases that organize prior to nucleation and crystallization (shown right) of silicalite from a homogeneous reaction mixture. Small- and wide-angle X-ray scattering studies prove that for zeolites nucleation may be homogeneous or

Homogeneous and heterogeneous photoredox-catalyzed hydroxymethylation of ketones and keto esters: catalyst screening, chemoselectivity and dilution effects

Directory of Open Access Journals (Sweden)

Axel G. Griesbeck

2014-05-01

Full Text Available The homogeneous titanium- and dye-catalyzed as well as the heterogeneous semiconductor particle-catalyzed photohydroxymethylation of ketones by methanol were investigated in order to evaluate the most active photocatalyst system. Dialkoxytitanium dichlorides are the most efficient species for chemoselective hydroxymethylation of acetophenone as well as other aromatic and aliphatic ketones. Pinacol coupling is the dominant process for semiconductor catalysis and ketone reduction dominates the Ti(OiPr4/methanol or isopropanol systems. Application of dilution effects on the TiO2 catalysis leads to an increase in hydroxymethylation at the expense of the pinacol coupling.

Introduction to chemical reaction engineering

International Nuclear Information System (INIS)

Kim, Yeong Geol

1990-10-01

This deals with chemical reaction engineering with thirteen chapters. The contents of this book are introduction on reaction engineering, chemical kinetics, thermodynamics and chemical reaction, abnormal reactor, non-isothermal reactor, nonideal reactor, catalysis in nonuniform system, diffusion and reaction in porosity catalyst, design catalyst heterogeneous reactor in solid bed, a high molecule polymerization, bio reaction engineering, reaction engineering in material process, control multi-variable reactor process using digital computer.

New and future developments in catalysis batteries, hydrogen storage and fuel cells

CERN Document Server

Suib, Steven L

2013-01-01

New and Future Developments in Catalysis is a package of seven books that compile the latest ideas concerning alternate and renewable energy sources and the role that catalysis plays in converting new renewable feedstock into biofuels and biochemicals. Both homogeneous and heterogeneous catalysts and catalytic processes will be discussed in a unified and comprehensive approach. There will be extensive cross-referencing within all volumes. Batteries and fuel cells are considered to be environmentally friendly devices for storage and production of electricity, and they are gaining considerable attention. The preparation of the feed for fuel cells (fuel) as well as the catalysts and the various conversion processes taking place in these devices are covered in this volume, together with the catalytic processes for hydrogen generation and storage. An economic analysis of the various processes is also part of this volume and enables an informed choice of the most suitable process. Offers in-depth coverage of all ca...

Theoretical mo delling of nanoparticles with applications to catalysis and sustainable energy

DEFF Research Database (Denmark)

Brodersen, Simon Hedegaard

The aim of this thesis is to gain a better understanding of the shape and structure of nanoparticles. Nanoparticles are important in heterogeneous catalysis, where the chemical reaction happens at the surface, since they maximise the available surface area for a given amount of catalyst. Studies...

Melting Heat in Radiative Flow of Carbon Nanotubes with Homogeneous-Heterogeneous Reactions

Science.gov (United States)

Hayat, Tasawar; Muhammad, Khursheed; Muhammad, Taseer; Alsaedi, Ahmed

2018-04-01

The present article provides mathematical modeling for melting heat and thermal radiation in stagnation-point flow of carbon nanotubes towards a nonlinear stretchable surface of variable thickness. The process of homogeneous-heterogeneous reactions is considered. Diffusion coefficients are considered equal for both reactant and autocatalyst. Water and gasoline oil are taken as base fluids. The conversion of partial differential system to ordinary differential system is done by suitable transformations. Optimal homotopy technique is employed for the solutions development of velocity, temperature, concentration, skin friction and local Nusselt number. Graphical results for various values of pertinent parameters are displayed and discussed. Our results indicate that the skin friction coefficient and local Nusselt number are enhanced for larger values of nanoparticles volume fraction.

Morphology-controlled synthesis of silver nanostructures via a seed catalysis process

Energy Technology Data Exchange (ETDEWEB)

Chen Chang; Wang Li; Yu Haojie; Wang Jianjun; Zhou Junfeng; Tan Qiaohua; Deng Libo [State Key Laboratory of Polymer Reaction Engineering, Zhejiang University, Hangzhou 310027 (China)

2007-03-21

A novel, effective strategy named 'seed catalysis' has been described here to synthesize silver nanostructures with controllable morphology. Typically, we added Na{sub 2}S into the reaction system and the Ag{sub 2}S semiconductor colloids formed at the initial stage would act as both seeds and catalyst in the silver reduction. The morphology of products is controlled by the concentration of Na{sub 2}S added to the system. Low concentration of Na{sub 2}S gives nanocubes of 40-50 nm in size, while a high concentration of Na{sub 2}S is of benefit to obtain nanowires. The growth of the silver crystal is also accelerated by the catalysis of Ag{sub 2}S. Electron microscopy and UV-vis absorption spectra have been used to investigate the evolution of silver nanowires, and a reasonable mechanism to explain the role of Ag{sub 2}S seeds has also been suggested. This semiconductor seed catalysis strategy will provide wide applications in the fabrication of metal nanomaterials.

On the Brønsted acid-catalyzed homogeneous hydrolysis of furans.

Science.gov (United States)

Nikbin, Nima; Caratzoulas, Stavros; Vlachos, Dionisios G

2013-11-01

Furan affairs: Electronic structure calculations of the homogeneous Brønsted acid-catalyzed hydrolysis of 2,5-dimethylfuran show that proton transfer to the β-position is rate-limiting and provides support that the hydrolysis follows general acid catalysis. By means of projected Fukui indices, we show this to be the case for unsubstituted, 2-, and 2,5-substituted furans with electron-donating groups. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molecular ingredients of heterogeneous catalysis

International Nuclear Information System (INIS)

Somorjai, G.A.

1982-06-01

The purpose of this paper is to present a review and status report to those in theoretical chemistry of the rapidly developing surface science of heterogeneous catalysis. The art of catalysis is developing into science. This profound change provides one with opportunities not only to understand the molecular ingredients of important catalytic systems but also to develop new and improved catalyst. The participation of theorists to find answers to important questions is sorely needed for the sound development of the field. It is the authors hope that some of the outstanding problems of heterogeneous catalysis that are identified in this paper will be investigated. For this purpose the paper is divided into several sections. The brief Introduction to the methodology and recent results of the surface science of heterogeneous catalysis is followed by a review of the concepts of heterogeneous catalysis. Then, the experimental results that identified the three molecular ingredients of catalysis, structure, carbonaceous deposit and the oxidation state of surface atoms are described. Each section is closed with a summary and a list of problems that require theoretical and experimental scrutiny. Finally attempts to build new catalyst systems and the theoretical and experimental problems that appeared in the course of this research are described

Molecular ingredients of heterogeneous catalysis

Energy Technology Data Exchange (ETDEWEB)

Somorjai, G.A.

1982-06-01

The purpose of this paper is to present a review and status report to those in theoretical chemistry of the rapidly developing surface science of heterogeneous catalysis. The art of catalysis is developing into science. This profound change provides one with opportunities not only to understand the molecular ingredients of important catalytic systems but also to develop new and improved catalyst. The participation of theorists to find answers to important questions is sorely needed for the sound development of the field. It is the authors hope that some of the outstanding problems of heterogeneous catalysis that are identified in this paper will be investigated. For this purpose the paper is divided into several sections. The brief Introduction to the methodology and recent results of the surface science of heterogeneous catalysis is followed by a review of the concepts of heterogeneous catalysis. Then, the experimental results that identified the three molecular ingredients of catalysis, structure, carbonaceous deposit and the oxidation state of surface atoms are described. Each section is closed with a summary and a list of problems that require theoretical and experimental scrutiny. Finally attempts to build new catalyst systems and the theoretical and experimental problems that appeared in the course of this research are described.

Comparison of the role that entropy has played in processes of non-enzymatic and enzymatic catalysis

International Nuclear Information System (INIS)

Dixon Pineda, Manuel Tomas

2012-01-01

The function that entropy has played is compared in processes of non-enzymatic and enzymatic catalysis. The processes followed are showed: the kinetics of the acid hydrolysis of 3-pentyl acetate and cyclopentyl acetate catalyzed by hydrochloric acid and enzymatic hydrolysis of ethyl acetate and γ-butyrolactone catalyzed by pig liver esterase. The activation parameters of Eyring were determined for each process and interpreted the contribution of the entropy of activation for catalysis in this type of model reactions. (author) [es

Base metal complexes as homogeneous catalysts and enzyme mimics.

Science.gov (United States)

Hu, Xile

2011-01-01

This article is a short overview of some recent research activity in the Laboratory of Inorganic Synthesis and Catalysis (LSCI) at EPFL-ISIC. It summarizes the work on Ni-catalyzed cross-coupling reactions of non-activated alkyl halides. It then describes and discusses the work on the bio-mimetic chemistry of [Fe]-hydrogenase.

Spatial homogenization method based on the inverse problem

International Nuclear Information System (INIS)

Tóta, Ádám; Makai, Mihály

2015-01-01

Highlights: • We derive a spatial homogenization method in slab and cylindrical geometries. • The fluxes and the currents on the boundary are preserved. • The reaction rates and the integral of the fluxes are preserved. • We present verification computations utilizing two- and four-energy groups. - Abstract: We present a method for deriving homogeneous multi-group cross sections to replace a heterogeneous region’s multi-group cross sections; providing that the fluxes, the currents on the external boundary, the reaction rates and the integral of the fluxes are preserved. We consider one-dimensional geometries: a symmetric slab and a homogeneous cylinder. Assuming that the boundary fluxes are given, two response matrices (RMs) can be defined concerning the current and the flux integral. The first one derives the boundary currents from the boundary fluxes, while the second one derives the flux integrals from the boundary fluxes. Further RMs can be defined that connects reaction rates to the boundary fluxes. Assuming that these matrices are known, we present formulae that reconstruct the multi-group diffusion cross-section matrix, the diffusion coefficients and the reaction cross sections in case of one-dimensional (1D) homogeneous regions. We apply these formulae to 1D heterogeneous regions and thus obtain a homogenization method. This method produces such an equivalent homogeneous material, that the fluxes and the currents on the external boundary, the reaction rates and the integral of the fluxes are preserved for any boundary fluxes. We carry out the exact derivations in 1D slab and cylindrical geometries. Verification computations for the presented homogenization method were performed using two- and four-group material cross sections, both in a slab and in a cylindrical geometry

Monopole catalysis: an overview

International Nuclear Information System (INIS)

Dawson, S.

1983-11-01

A summary of the talks presented in the topological workshop on monopole catalysis at this conference is given. We place special emphasis on the conservation laws which determine the allowed monopole-fermion interactions and on catalysis as a probe of the structure of a grand unified theory. 11 references

Heterogeneously Catalysed Chemical Reactions in Carbon Dioxide Medium

DEFF Research Database (Denmark)

Musko, Nikolai E.

In this PhD-study the different areas of chemical engineering, heterogeneous catalysis, supercritical fluids, and phase equilibrium thermodynamics have been brought together for selected reactions. To exploit the beneficial properties of supercritical fluids in heterogeneous catalysis, experimental...... studies of catalytic chemical reactions in dense and supercritical carbon dioxide have been complemented by the theoretical calculations of phase equilibria using advanced thermodynamic models. In the recent years, the use of compressed carbon dioxide as innovative, non-toxic and non-flammable, cheap......, and widely available reaction medium for many practical and industrial applications has drastically increased. Particularly attractive are heterogeneously catalysed chemical reactions. The beneficial use of CO2 is attributed to its unique properties at dense and supercritical states (at temperatures...

Homogeneous and Heterogeneous Reaction and Transformation of Hg and Trace Metals in Combustion Systems

Energy Technology Data Exchange (ETDEWEB)

J. Helble; Clara Smith; David Miller

2009-08-31

The overall goal of this project was to produce a working dynamic model to predict the transformation and partitioning of trace metals resulting from combustion of a broad range of fuels. The information provided from this model will be instrumental in efforts to identify fuels and conditions that can be varied to reduce metal emissions. Through the course of this project, it was determined that mercury (Hg) and arsenic (As) would be the focus of the experimental investigation. Experiments were therefore conducted to examine homogeneous and heterogeneous mercury oxidation pathways, and to assess potential interactions between arsenic and calcium. As described in this report, results indicated that the role of SO{sub 2} on Hg oxidation was complex and depended upon overall gas phase chemistry, that iron oxide (hematite) particles contributed directly to heterogeneous Hg oxidation, and that As-Ca interactions occurred through both gas-solid and within-char reaction pathways. Modeling based on this study indicated that, depending upon coal type and fly ash particle size, vaporization-condensation, vaporization-surface reaction, and As-CaO in-char reaction all play a role in arsenic transformations under combustion conditions.

Numerical tackling for viscoelastic fluid flow in rotating frame considering homogeneous-heterogeneous reactions

Science.gov (United States)

Maqsood, Najwa; Mustafa, M.; Khan, Junaid Ahmad

This study provides a numerical treatment for rotating flow of viscoelastic (Maxwell) fluid bounded by a linearly deforming elastic surface. Mass transfer analysis is carried out in the existence of homogeneous-heterogeneous reactions. By means of usual transformation, the governing equations are changed into global similarity equations which have been tackled by an expedient shooting approach. A contemporary numerical routine bvp4c of software MATLAB is also opted to develop numerical approximations. Both methods of solution are found in complete agreement in all the cases. Velocity and concentration profiles are computed and elucidated for certain range of viscoelastic fluid parameter. The solutions contain a rotation-strength parameter λ that has a considerable impact on the flow fields. For sufficiently large value of λ , the velocity fields are oscillatory decaying function of the non-dimensional vertical distance. Concentration distribution at the surface is found to decrease upon increasing the strengths of chemical reactions. A comparison of present computations is made with those of already published ones and such comparison appears convincing.

Center for Catalysis at Iowa State University

Energy Technology Data Exchange (ETDEWEB)

Kraus, George A.

2006-10-17

The overall objective of this proposal is to enable Iowa State University to establish a Center that enjoys world-class stature and eventually enhances the economy through the transfer of innovation from the laboratory to the marketplace. The funds have been used to support experimental proposals from interdisciplinary research teams in areas related to catalysis and green chemistry. Specific focus areas included: • Catalytic conversion of renewable natural resources to industrial materials • Development of new catalysts for the oxidation or reduction of commodity chemicals • Use of enzymes and microorganisms in biocatalysis • Development of new, environmentally friendly reactions of industrial importance These focus areas intersect with barriers from the MYTP draft document. Specifically, section 2.4.3.1 Processing and Conversion has a list of bulleted items under Improved Chemical Conversions that includes new hydrogenation catalysts, milder oxidation catalysts, new catalysts for dehydration and selective bond cleavage catalysts. Specifically, the four sections are: 1. Catalyst development (7.4.12.A) 2. Conversion of glycerol (7.4.12.B) 3. Conversion of biodiesel (7.4.12.C) 4. Glucose from starch (7.4.12.D) All funded projects are part of a soybean or corn biorefinery. Two funded projects that have made significant progress toward goals of the MYTP draft document are: Catalysts to convert feedstocks with high fatty acid content to biodiesel (Kraus, Lin, Verkade) and Conversion of Glycerol into 1,3-Propanediol (Lin, Kraus). Currently, biodiesel is prepared using homogeneous base catalysis. However, as producers look for feedstocks other than soybean oil, such as waste restaurant oils and rendered animal fats, they have observed a large amount of free fatty acids contained in the feedstocks. Free fatty acids cannot be converted into biodiesel using homogeneous base-mediated processes. The CCAT catalyst system offers an integrated and cooperative catalytic

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.

Ruthenium complexes of chelating amido-functionalized N ...

Indian Academy of Sciences (India)

tric transfer hydrogenation reactions,5 metathesis,6 olefin epoxidation reactions,7 hydroformylation reac- tions,8 electrooxidation reactions,9 facial cycloaddition of azides with terminal alkynes regioselectively10 etc. to name a few. The phenomenal success of the N-heterocyclic car- benes in homogeneous catalysis, has ...

Numerical analysis of MHD Carreau fluid flow over a stretching cylinder with homogenous-heterogeneous reactions

Science.gov (United States)

Khan, Imad; Ullah, Shafquat; Malik, M. Y.; Hussain, Arif

2018-06-01

The current analysis concentrates on the numerical solution of MHD Carreau fluid flow over a stretching cylinder under the influences of homogeneous-heterogeneous reactions. Modelled non-linear partial differential equations are converted into ordinary differential equations by using suitable transformations. The resulting system of equations is solved with the aid of shooting algorithm supported by fifth order Runge-Kutta integration scheme. The impact of non-dimensional governing parameters on the velocity, temperature, skin friction coefficient and local Nusselt number are comprehensively delineated with the help of graphs and tables.

Numerical study for melting heat transfer and homogeneous-heterogeneous reactions in flow involving carbon nanotubes

Science.gov (United States)

Hayat, Tasawar; Muhammad, Khursheed; Alsaedi, Ahmed; Asghar, Saleem

2018-03-01

Present work concentrates on melting heat transfer in three-dimensional flow of nanofluid over an impermeable stretchable surface. Analysis is made in presence of porous medium and homogeneous-heterogeneous reactions. Single and multi-wall CNTs (carbon nanotubes) are considered. Water is chosen as basefluid. Adequate transformations yield the non-linear ordinary differential systems. Solution of emerging problems is obtained using shooting method. Impacts of influential variables on velocity and temperature are discussed graphically. Skin friction coefficient and Nusselt number are numerically discussed. The results for MWCNTs and SWCNTs are compared and examined.

Parallel array of nanochannels grafted with polymer-brushes-stabilized Au nanoparticles for flow-through catalysis.

Science.gov (United States)

Liu, Jianxi; Ma, Shuanhong; Wei, Qiangbing; Jia, Lei; Yu, Bo; Wang, Daoai; Zhou, Feng

2013-12-07

Smart systems on the nanometer scale for continuous flow-through reaction present fascinating advantages in heterogeneous catalysis, in which a parallel array of straight nanochannels offers a platform with high surface area for assembling and stabilizing metallic nanoparticles working as catalysts. Herein we demonstrate a method for finely modifying the nanoporous anodic aluminum oxide (AAO), and further integration of nanoreactors. By using atomic transfer radical polymerization (ATRP), polymer brushes were successfully grafted on the inner wall of the nanochannels of the AAO membrane, followed by exchanging counter ions with a precursor for nanoparticles (NPs), and used as the template for deposition of well-defined Au NPs. The membrane was used as a functional nanochannel for novel flow-through catalysis. High catalytic performance and instantaneous separation of products from the reaction system was achieved in reduction of 4-nitrophenol.

Parallel array of nanochannels grafted with polymer-brushes-stabilized Au nanoparticles for flow-through catalysis

Science.gov (United States)

Liu, Jianxi; Ma, Shuanhong; Wei, Qiangbing; Jia, Lei; Yu, Bo; Wang, Daoai; Zhou, Feng

2013-11-01

Smart systems on the nanometer scale for continuous flow-through reaction present fascinating advantages in heterogeneous catalysis, in which a parallel array of straight nanochannels offers a platform with high surface area for assembling and stabilizing metallic nanoparticles working as catalysts. Herein we demonstrate a method for finely modifying the nanoporous anodic aluminum oxide (AAO), and further integration of nanoreactors. By using atomic transfer radical polymerization (ATRP), polymer brushes were successfully grafted on the inner wall of the nanochannels of the AAO membrane, followed by exchanging counter ions with a precursor for nanoparticles (NPs), and used as the template for deposition of well-defined Au NPs. The membrane was used as a functional nanochannel for novel flow-through catalysis. High catalytic performance and instantaneous separation of products from the reaction system was achieved in reduction of 4-nitrophenol.

Synergistic dual activation catalysis by palladium nanoparticles for epoxide ring opening with phenols.

Science.gov (United States)

Seth, Kapileswar; Roy, Sudipta Raha; Pipaliya, Bhavin V; Chakraborti, Asit K

2013-07-04

Synergistic dual activation catalysis has been devised for epoxide phenolysis wherein palladium nanoparticles induce electrophilic activation via coordination with the epoxide oxygen followed by nucleophilic activation through anion-π interaction with the aromatic ring of the phenol, and water (reaction medium) also renders assistance through 'epoxide-phenol' dual activation.

Catalysis for alternative energy generation

CERN Document Server

2012-01-01

Summarizes recent problems in using catalysts in alternative energy generation and proposes novel solutions  Reconsiders the role of catalysis in alternative energy generation  Contributors include catalysis and alternative energy experts from across the globe

Proton Mediated Chemistry and Catalysis in a Self-Assembled Supramolecular Host

Energy Technology Data Exchange (ETDEWEB)

Pluth, Michael; Bergman, Robert; Raymond, Kenneth

2009-04-10

Synthetic supramolecular host assemblies can impart unique reactivity to encapsulated guest molecules. Synthetic host molecules have been developed to carry out complex reactions within their cavities, despite the fact that they lack the type of specifically tailored functional groups normally located in the analogous active sites of enzymes. Over the past decade, the Raymond group has developed a series of self-assembled supramolecules and the Bergman group has developed and studied a number of catalytic transformations. In this Account, we detail recent collaborative work between these two groups, focusing on chemical catalysis stemming from the encapsulation of protonated guests and expanding to acid catalysis in basic solution. We initially investigated the ability of a water-soluble, self-assembled supramolecular host molecule to encapsulate protonated guests in its hydrophobic core. Our study of encapsulated protonated amines revealed rich host-guest chemistry. We established that self-exchange (that is, in-out guest movement) rates of protonated amines were dependent on the steric bulk of the amine rather than its basicity. The host molecule has purely rotational tetrahedral (T) symmetry, so guests with geminal N-methyl groups (and their attendant mirror plane) were effectively desymmetrized; this allowed for the observation and quantification of the barriers for nitrogen inversion followed by bond rotation. Furthermore, small nitrogen heterocycles, such as N-alkylaziridines, N-alkylazetidines, and N-alkylpyrrolidines, were found to be encapsulated as proton-bound homodimers or homotrimers. We further investigated the thermodynamic stabilization of protonated amines, showing that encapsulation makes the amines more basic in the cavity. Encapsulation raises the effective basicity of protonated amines by up to 4.5 pK{sub a} units, a difference almost as large as that between the moderate and strong bases carbonate and hydroxide. The thermodynamic stabilization

Proton-Mediated Chemistry and Catalysis in a Self-Assembled Supramolecular Host

International Nuclear Information System (INIS)

Pluth, Michael; Bergman, Robert; Raymond, Kenneth

2009-01-01

Synthetic supramolecular host assemblies can impart unique reactivity to encapsulated guest molecules. Synthetic host molecules have been developed to carry out complex reactions within their cavities, despite the fact that they lack the type of specifically tailored functional groups normally located in the analogous active sites of enzymes. Over the past decade, the Raymond group has developed a series of self-assembled supramolecules and the Bergman group has developed and studied a number of catalytic transformations. In this Account, we detail recent collaborative work between these two groups, focusing on chemical catalysis stemming from the encapsulation of protonated guests and expanding to acid catalysis in basic solution. We initially investigated the ability of a water-soluble, self-assembled supramolecular host molecule to encapsulate protonated guests in its hydrophobic core. Our study of encapsulated protonated amines revealed rich host-guest chemistry. We established that self-exchange (that is, in-out guest movement) rates of protonated amines were dependent on the steric bulk of the amine rather than its basicity. The host molecule has purely rotational tetrahedral (T) symmetry, so guests with geminal N-methyl groups (and their attendant mirror plane) were effectively desymmetrized; this allowed for the observation and quantification of the barriers for nitrogen inversion followed by bond rotation. Furthermore, small nitrogen heterocycles, such as N-alkylaziridines, N-alkylazetidines, and N-alkylpyrrolidines, were found to be encapsulated as proton-bound homodimers or homotrimers. We further investigated the thermodynamic stabilization of protonated amines, showing that encapsulation makes the amines more basic in the cavity. Encapsulation raises the effective basicity of protonated amines by up to 4.5 pK a units, a difference almost as large as that between the moderate and strong bases carbonate and hydroxide. The thermodynamic stabilization of

Soybean epoxide production with in situ peracetic acid using homogeneous catalysis

Directory of Open Access Journals (Sweden)

Luis Alejandro Boyacá Mendivelso

2010-01-01

Full Text Available Using vegetable oils has become an excellent option for petrochemical product substitution. The epoxides obtained from such oils have wide applications as plastifiers and PVC stabilisers and as raw material in polyol synthesis for the polyurethane industry. This paper presents soybean oil epoxidation using a homogeneous catalyst in a well-mixed, stirred reactor being operated in iso- thermal conditions. The best result achieved was a 6.4% oxyrane oxygen content using hydrogen peroxide (25% molar excess, a- cetic acid (5% p/p and sulphuric acid (2% p/p concentrations at 80°C.

Editorial: Nanoscience makes catalysis greener

KAUST Repository

Polshettiwar, Vivek; Basset, Jean-Marie; Astruc, Didier

2012-01-01

Green chemistry by nanocatalysis: Catalysis is a strategic field of science because it involves new ways of meeting energy and sustainability challenges. The concept of green chemistry, which makes the science of catalysis even more creative, has

Solid acid catalysis from fundamentals to applications

CERN Document Server

Hattori, Hideshi

2014-01-01

IntroductionTypes of solid acid catalystsAdvantages of solid acid catalysts Historical overviews of solid acid catalystsFuture outlookSolid Acids CatalysisDefinition of acid and base -Brnsted acid and Lewis acid-Acid sites on surfacesAcid strengthRole of acid sites in catalysisBifunctional catalysisPore size effect on catalysis -shape selectivity-Characterization of Solid Acid Catalysts Indicator methodTemperature programmed desorption (TPD) of ammoniaCalorimetry of adsorption of basic moleculesInfrare

Neutrons for Catalysis: A Workshop on Neutron Scattering Techniques for Studies in Catalysis

International Nuclear Information System (INIS)

Overbury, Steven H.; Coates, Leighton; Herwig, Kenneth W.; Kidder, Michelle

2011-01-01

This report summarizes the Workshop on Neutron Scattering Techniques for Studies in Catalysis, held at the Spallation Neutron Source (SNS) at Oak Ridge National Laboratory (ORNL) on September 16 and 17, 2010. The goal of the Workshop was to bring experts in heterogeneous catalysis and biocatalysis together with neutron scattering experimenters to identify ways to attack new problems, especially Grand Challenge problems in catalysis, using neutron scattering. The Workshop locale was motivated by the neutron capabilities at ORNL, including the High Flux Isotope Reactor (HFIR) and the new and developing instrumentation at the SNS. Approximately 90 researchers met for 1 1/2 days with oral presentations and breakout sessions. Oral presentations were divided into five topical sessions aimed at a discussion of Grand Challenge problems in catalysis, dynamics studies, structure characterization, biocatalysis, and computational methods. Eleven internationally known invited experts spoke in these sessions. The Workshop was intended both to educate catalyst experts about the methods and possibilities of neutron methods and to educate the neutron community about the methods and scientific challenges in catalysis. Above all, it was intended to inspire new research ideas among the attendees. All attendees were asked to participate in one or more of three breakout sessions to share ideas and propose new experiments that could be performed using the ORNL neutron facilities. The Workshop was expected to lead to proposals for beam time at either the HFIR or the SNS; therefore, it was expected that each breakout session would identify a few experiments or proof-of-principle experiments and a leader who would pursue a proposal after the Workshop. Also, a refereed review article will be submitted to a prominent journal to present research and ideas illustrating the benefits and possibilities of neutron methods for catalysis research.

Neutrons for Catalysis: A Workshop on Neutron Scattering Techniques for Studies in Catalysis

Energy Technology Data Exchange (ETDEWEB)

Overbury, Steven {Steve} H [ORNL; Coates, Leighton [ORNL; Herwig, Kenneth W [ORNL; Kidder, Michelle [ORNL

2011-10-01

This report summarizes the Workshop on Neutron Scattering Techniques for Studies in Catalysis, held at the Spallation Neutron Source (SNS) at Oak Ridge National Laboratory (ORNL) on September 16 and 17, 2010. The goal of the Workshop was to bring experts in heterogeneous catalysis and biocatalysis together with neutron scattering experimenters to identify ways to attack new problems, especially Grand Challenge problems in catalysis, using neutron scattering. The Workshop locale was motivated by the neutron capabilities at ORNL, including the High Flux Isotope Reactor (HFIR) and the new and developing instrumentation at the SNS. Approximately 90 researchers met for 1 1/2 days with oral presentations and breakout sessions. Oral presentations were divided into five topical sessions aimed at a discussion of Grand Challenge problems in catalysis, dynamics studies, structure characterization, biocatalysis, and computational methods. Eleven internationally known invited experts spoke in these sessions. The Workshop was intended both to educate catalyst experts about the methods and possibilities of neutron methods and to educate the neutron community about the methods and scientific challenges in catalysis. Above all, it was intended to inspire new research ideas among the attendees. All attendees were asked to participate in one or more of three breakout sessions to share ideas and propose new experiments that could be performed using the ORNL neutron facilities. The Workshop was expected to lead to proposals for beam time at either the HFIR or the SNS; therefore, it was expected that each breakout session would identify a few experiments or proof-of-principle experiments and a leader who would pursue a proposal after the Workshop. Also, a refereed review article will be submitted to a prominent journal to present research and ideas illustrating the benefits and possibilities of neutron methods for catalysis research.

Computational Design of Clusters for Catalysis

Science.gov (United States)

Jimenez-Izal, Elisa; Alexandrova, Anastassia N.

2018-04-01

When small clusters are studied in chemical physics or physical chemistry, one perhaps thinks of the fundamental aspects of cluster electronic structure, or precision spectroscopy in ultracold molecular beams. However, small clusters are also of interest in catalysis, where the cold ground state or an isolated cluster may not even be the right starting point. Instead, the big question is: What happens to cluster-based catalysts under real conditions of catalysis, such as high temperature and coverage with reagents? Myriads of metastable cluster states become accessible, the entire system is dynamic, and catalysis may be driven by rare sites present only under those conditions. Activity, selectivity, and stability are highly dependent on size, composition, shape, support, and environment. To probe and master cluster catalysis, sophisticated tools are being developed for precision synthesis, operando measurements, and multiscale modeling. This review intends to tell the messy story of clusters in catalysis.

Thermoswitchable catalysis controlled by reversible dispersion/aggregation change of nanoreactors in the presence of α-CD polymers

Science.gov (United States)

Li, Yinfeng; Hu, Jie; Niu, Chengrong; Leng, Jinghang; Li, Songjun

2018-06-01

The present work was aimed at preparing a thermosensitive nanoreactor system which could adjust its dispersion/aggregation status according to external temperature change to achieve the switchable catalysis. The mesoporous silica nanoparticle (MSNP) was selected as the framework material of the nanoreactor, and Ag nanoparticles were encapsulated in the mesoporous silica by an in situ reaction. Dodecyl groups were introduced onto MSNP surface, which could transform reversibly between complexation and disassociation with α-cyclodextrin (CD) cavity upon temperature change. It was found that the nanoreactors aggregated and the catalysis was effectively switched ‘off’ in the presence of CD polymers at low temperature (20 °C). However, when the temperature increased to 50 °C, the nanoreactors redispersed and catalysis successfully switched ‘on’.

Coal-related research, organic chemistry, and catalysis

International Nuclear Information System (INIS)

Anon.

1980-01-01

Coal chemistry research topics included: H exchange at 400 0 C, breaking C-C bonds in coal, molecular weight estimation using small-angle neutron scattering, 13 C NMR spectra of coals, and tunneling during H/D isotope effects. Studies of coal conversion chemistry included thermolysis of bibenzyl and 1-naphthol, heating of coals in phenol, advanced indirect liquefaction based on Koelbel slurry Fischer-Tropsch reactor, and plasma oxidation of coal minerals. Reactions of PAHs in molten SbCl 3 , a hydrocracking catalyst, were studied. Finally, heterogeneous catalysis (desulfurization etc.) was studied using Cu, Au, and Ni surfaces. 7 figures, 6 tables

Iron-Catalyzed C-O Bond Activation: Opportunity for Sustainable Catalysis.

Science.gov (United States)

Bisz, Elwira; Szostak, Michal

2017-10-23

Oxygen-based electrophiles have emerged as some of the most valuable cross-coupling partners in organic synthesis due to several major strategic and environmental benefits, such as abundance and potential to avoid toxic halide waste. In this context, iron-catalyzed C-O activation/cross-coupling holds particular promise to achieve sustainable catalytic protocols due to its natural abundance, inherent low toxicity, and excellent economic and ecological profile. Recently, tremendous progress has been achieved in the development of new methods for functional-group-tolerant iron-catalyzed cross-coupling reactions by selective C-O cleavage. These methods establish highly attractive alternatives to traditional cross-coupling reactions by using halides as electrophilic partners. In particular, new easily accessible oxygen-based electrophiles have emerged as substrates in iron-catalyzed cross-coupling reactions, which significantly broaden the scope of this catalysis platform. New mechanistic manifolds involving iron catalysis have been established; thus opening up vistas for the development of a wide range of unprecedented reactions. The synthetic potential of this sustainable mode of reactivity has been highlighted by the development of new strategies in the construction of complex motifs, including in target synthesis. The most recent advances in sustainable iron-catalyzed cross-coupling of C-O-based electrophiles are reviewed, with a focus on both mechanistic aspects and synthetic utility. It should be noted that this catalytic manifold provides access to motifs that are often not easily available by other methods, such as the assembly of stereodefined dienes or C(sp 2 )-C(sp 3 ) cross-couplings, thus emphasizing the synthetic importance of this mode of reactivity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ruthenium nanocatalysis on redox reactions.

Science.gov (United States)

Veerakumar, Pitchaimani; Ramdass, Arumugam; Rajagopal, Seenivasan

2013-07-01

Nanoparticles have generated intense interest over the past 20 years due to their high potential applications in different areas such as catalysis, sensors, nanoscale electronics, fuel and solar cells and optoelectronics. As the large fractions of metal atoms are exposed to the surface, the use of metal nanoparticles as nanocatalysts allows mild reaction conditions and high catalytic efficiency in a large number of chemical transformations. They have emerged as sustainable heterogeneous catalysts and catalyst supports alternative to conventional materials. This review focuses on the synthesis, characterization and catalytic role of ruthenium nanoparticles (RuNPs) on the redox reactions of heteroatom containing organic compounds with the green reagent H2O2, a field that has attracted immense interest among the chemical, materials and industrial communities. We intend to present a broad overview of Ru nanocatalysts for redox reactions with an emphasis on their performance, stability and reusability. The growth in the chemistry of organic sulfoxides and N-oxides during last decade was due to their importance as synthetic intermediates for the production of a wide range of chemically and biologically active molecules. Thus design of efficient methods for the synthesis of sulfoxides and N-oxides becomes important. This review concentrates on the catalysis of RuNPs on the H2O2 oxidation of organic sulfides to sulfoxides and amines to N-oxides. The deoxygenation reactions of sulfoxides to sulfides and reduction of nitro compounds to amines are fundamental reactions in both chemistry and biology. Here, we also highlight the catalysis of metal nanoparticles on the deoxygenation of sulfoxides and sulfones and reduction of nitro compounds with particular emphasis on the mechanistic aspects.

Catalysis in flow microreactors with wall coatings of acidic polymer brushes and dendrimer-encapsulated nanoparticles

NARCIS (Netherlands)

Ricciardi, R.

2015-01-01

Continuous-flow microreactors are an invaluable tool to carry out organic reactions owing to their numerous advantages with respect to batch scale synthesis. In particular, supported catalysts enable heterogeneous catalysis to be conducted in an efficient way. In this thesis, the development and

Quantitative Analysis of Homogeneous Electrocatalytic Reactions at IDA Electrodes: The Example of [Ni(PPh2NBn2)2]2+

Energy Technology Data Exchange (ETDEWEB)

Liu, Fei; Parkinson, B. A.; Divan, Ralu; Roberts, John; Liang, Yanping

2016-12-01

Interdigitated array (IDA) electrodes have been applied to study the EC’ (electron transfer reaction followed by a catalytic reaction) reactions and a new method of quantitative analysis of IDA results was developed. In this new method, currents on IDA generator and collector electrodes for an EC’ mechanism are derived from the number of redox cycles and the contribution of non-catalytic current. And the fractions of bipotential recycling species and catalytic-active species are calculated, which helps understanding the catalytic reaction mechanism. The homogeneous hydrogen evolution reaction catalyzed by [Ni(PPh2NBn2)2]2+ (where PPh2NBn2 is 1,5-dibenzyl-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) electrocatalyst was examined and analyzed with IDA electrodes. Besides, the existence of reaction intermediates in the catalytic cycle is inferred from the electrochemical behavior of a glassy carbon disk electrodes and carbon IDA electrodes. This quantitative analysis of IDA electrode cyclic voltammetry currents can be used as a simple and straightforward method for determining reaction mechanism in other catalytic systems as well.

Quantitative Analysis of Homogeneous Electrocatalytic Reactions at IDA Electrodes: The Example of [Ni(PPh2NBn2)2]2+

International Nuclear Information System (INIS)

Liu, Fei; Parkinson, B.A.; Divan, Ralu; Roberts, John; Liang, Yanping

2016-01-01

Interdigitated array (IDA) electrodes have been applied to study the EC’ (electron transfer reaction followed by a catalytic reaction) reactions and a new method of quantitative analysis of IDA results was developed. In this new method, currents on IDA generator and collector electrodes for an EC’ mechanism are derived from the number of redox cycles and the contribution of non-catalytic current. And the fractions of bipotential recycling species and catalytic-active species are calculated, which helps understanding the catalytic reaction mechanism. The homogeneous hydrogen evolution reaction catalyzed by [Ni(P Ph 2 N Bn 2 ) 2 ] 2+ (where P Ph 2 N Bn 2 is 1,5-dibenzyl-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) electrocatalyst was examined and analyzed with IDA electrodes. Besides, the existence of reaction intermediates in the catalytic cycle is inferred from the electrochemical behavior of a glassy carbon disk electrodes and carbon IDA electrodes. This quantitative analysis of IDA electrode cyclic voltammetry currents can be used as a simple and straightforward method for determining reaction mechanism in other catalytic systems as well.

Catálise assimétrica na ciclopropanação de olefinas Asymmetric catalysis in the cyclopropanation of olefins

Directory of Open Access Journals (Sweden)

Raquel A. C. Leão

2007-01-01

Full Text Available The main methodologies in the asymmetric cyclopropanation of alkenes with emphasis on asymmetric catalysis are covered. Exemples are the Simmons-Smith reaction, the use of diazoalkanes and reactions carried out by decomposition of alpha-diazoesters in the presence of transition metals.

Cosmic strings and baryon decay catalysis

Energy Technology Data Exchange (ETDEWEB)

Gregory, R.; Perkins, W.B.; Davis, A.C.; Brandenberger, R.H. (Fermi National Accelerator Lab., Batavia, IL (USA); Cambridge Univ. (UK); Brown Univ., Providence, RI (USA). Dept. of Physics)

1989-09-01

Cosmic strings, like monopoles, can catalyze proton decay. For integer charged fermions, the cross section for catalysis is not amplified, unlike in the case of monopoles. We review the catalysis processes both in the free quark and skyrmion pictures and discuss the implications for baryogenesis. We present a computation of the cross section for monopole catalyzed skyrmion decay using classical physics. We also discuss some effects which can screen catalysis processes. 32 refs., 1 fig.

Cosmic strings and baryon decay catalysis

International Nuclear Information System (INIS)

Gregory, R.; Perkins, W.B.; Davis, A.C.; Brandenberger, R.H.; Cambridge Univ.; Brown Univ., Providence, RI

1989-09-01

Cosmic strings, like monopoles, can catalyze proton decay. For integer charged fermions, the cross section for catalysis is not amplified, unlike in the case of monopoles. We review the catalysis processes both in the free quark and skyrmion pictures and discuss the implications for baryogenesis. We present a computation of the cross section for monopole catalyzed skyrmion decay using classical physics. We also discuss some effects which can screen catalysis processes. 32 refs., 1 fig

Design of a new reactor-like high temperature near ambient pressure scanning tunneling microscope for catalysis studies.

Science.gov (United States)

Tao, Franklin Feng; Nguyen, Luan; Zhang, Shiran

2013-03-01

Here, we present the design of a new reactor-like high-temperature near ambient pressure scanning tunneling microscope (HT-NAP-STM) for catalysis studies. This HT-NAP-STM was designed for exploration of structures of catalyst surfaces at atomic scale during catalysis or under reaction conditions. In this HT-NAP-STM, the minimized reactor with a volume of reactant gases of ∼10 ml is thermally isolated from the STM room through a shielding dome installed between the reactor and STM room. An aperture on the dome was made to allow tip to approach to or retract from a catalyst surface in the reactor. This dome minimizes thermal diffusion from hot gas of the reactor to the STM room and thus remains STM head at a constant temperature near to room temperature, allowing observation of surface structures at atomic scale under reaction conditions or during catalysis with minimized thermal drift. The integrated quadrupole mass spectrometer can simultaneously measure products during visualization of surface structure of a catalyst. This synergy allows building an intrinsic correlation between surface structure and its catalytic performance. This correlation offers important insights for understanding of catalysis. Tests were done on graphite in ambient environment, Pt(111) in CO, graphene on Ru(0001) in UHV at high temperature and gaseous environment at high temperature. Atom-resolved surface structure of graphene on Ru(0001) at 500 K in a gaseous environment of 25 Torr was identified.

Spectroscopy in catalysis : an introduction

NARCIS (Netherlands)

Niemantsverdriet, J.W.

2007-01-01

Spectroscopy in Catalysis is an introduction to the most important analytical techniques that are nowadays used in catalysis and in catalytic surface chemistry. The aim of the book is to give the reader a feeling for the type of information that characterization techniques provide about questions

Poly(Ionic Liquid: A New Phase in a Thermoregulated Phase Separated Catalysis and Catalyst Recycling System of Transition Metal-Mediated ATRP

Directory of Open Access Journals (Sweden)

Lan Yao

2018-03-01

Full Text Available Poly(ionic liquids (PILs have become the frontier domains in separation science because of the special properties of ionic liquids as well as their corresponding polymers. Considering their function in separation, we designed and synthesized a thermoregulated PIL. That is, this kind of PIL could separate with an organic phase which dissolves the monomers at ambient temperature. When heated to the reaction temperature, they become a homogeneous phase, and they separate again when the temperature falls to the ambient temperature after polymerization. Based on this, a thermoregulated phase separated catalysis (TPSC system for Cu-based atom transfer radical polymerization (ATRP was constructed. The copper catalyst (CuBr2 used here is easily separated and recycled in situ just by changing the temperature in this system. Moreover, even when the catalyst had been recycled five times, the controllability over resultant polymers is still satisfying. Finally, only 1~2 ppm metal catalyst was left in the polymer solution phase, which indicates the really high recycling efficiency.

Recent Progress in Asymmetric Catalysis and Chromatographic Separation by Chiral Metal–Organic Frameworks

Directory of Open Access Journals (Sweden)

Suchandra Bhattacharjee

2018-03-01

Full Text Available Metal–organic frameworks (MOFs, as a new class of porous solid materials, have emerged and their study has established itself very quickly into a productive research field. This short review recaps the recent advancement of chiral MOFs. Here, we present simple, well-ordered instances to classify the mode of synthesis of chiral MOFs, and later demonstrate the potential applications of chiral MOFs in heterogeneous asymmetric catalysis and enantioselective separation. The asymmetric catalysis sections are subdivided based on the types of reactions that have been successfully carried out recently by chiral MOFs. In the part on enantioselective separation, we present the potentiality of chiral MOFs as a stationary phase for high-performance liquid chromatography (HPLC and high-resolution gas chromatography (GC by considering fruitful examples from current research work. We anticipate that this review will provide interest to researchers to design new homochiral MOFs with even greater complexity and effort to execute their potential functions in several fields, such as asymmetric catalysis, enantiomer separation, and chiral recognition.

Active sites engineering of metal-organic frameworks for heterogeneous catalysis

Energy Technology Data Exchange (ETDEWEB)

Li, Xinle [Iowa State Univ., Ames, IA (United States)

2016-12-17

In conclusion, we have for the first time developed a novel solid base catalyst, Ndoped MOF-253 derived porous carbons (Cz-MOF-253). Cz-MOF-253 is highly porous and exhibit high efficiency in Knoevenagel condensation reaction. Furthermore, Cz-MOF-253 is robust and can be reused up to five times. In comparison, the analogous nitrogen-free catalyst-Cz-DUT-5, and other nitrogen- MOFs derived carbon showed an inferior performance. Moreover, the high basicity and porous nature enable the design of bifunctional catalyst and facilitate tandem condensation-hydrogenation reactions. This work delineates the first attempt that demonstrates MOF-derived carbons as solid base catalyst and its potential application in tandem catalysis. Future work on exploring new catalytic reactions based on such porous Lewis basic MOF-derived carbons is currently underway.

Dinuclear Tetrapyrazolyl Palladium Complexes Exhibiting Facile Tandem Transfer Hydrogenation/Suzuki Coupling Reaction of Fluoroarylketone

KAUST Repository

Dehury, Niranjan

2016-07-18

Herein, we report an unprecedented example of dinuclear pyrazolyl-based Pd complexes exhibiting facile tandem catalysis for fluoroarylketone: Tetrapyrazolyl di-palladium complexes with varying Pd-Pd distances efficiently catalyze the tandem reaction involving transfer hydrogenation of fluoroarylketone to the corresponding alcohol and Suzuki-Miyaura cross coupling reaction of the resulting fluoroarylalcohol under moderate reaction conditions, to biaryl alcohol. The complex with the shortest Pd-Pd distance exhibits the highest tandem activity among its di-metallic analogues, and exceeds in terms of activity and selectivity the analogous mononuclear compound. The kinetics of the reaction indicates clearly that reductive transformation of haloarylketone into haloaryalcohol is the rate determining step in the tandem reaction. Interestingly while fluoroarylketone undergoes the multistep tandem catalysis, the chloro- and bromo-arylketones undergo only a single step C-C coupling reaction resulting in biarylketone as the final product. Unlike the pyrazole based Pd compounds, the precursor PdCl2 and the phosphine based relevant complexes (PPh3)2PdCl2 and (PPh3)4Pd are found to be unable to exhibit the tandem catalysis.

Magnetic monopole catalysis of proton decay

International Nuclear Information System (INIS)

Marciano, W.J.; Salvino, D.

1986-09-01

Catalysis of proton decay by GUT magnetic monopoles (the Rubakov-Callan effect) is discussed. Combining a short-distance cross section calculation by Bernreuther and Craigie with the long-distance velocity dependent distortion factors of Arafune and Fukugita, catalysis rate predictions which can be compared with experiment are obtained. At present, hydrogen rich detectors such as water (H 2 O) and methane (CH 4 ) appear to be particularly well suited for observing catalysis by very slow monopoles. 17 refs., 1 fig

pincer complex in Suzuki–Miyaura cross-coupling reaction under

Indian Academy of Sciences (India)

The recent focus of interest on pincer complexes is due to their extended utility in the field of homogeneous catalysis.1 Pincer complexes offer interesting possibili- ties both in terms of mechanistic understanding and cat- alytic performance.1b The high catalytic efficiency is attributed to the stable and compact geometry of the.

Online screening of homogeneous catalyst performance using reaction detection mass spectrometry

NARCIS (Netherlands)

Martha, C.T.; Elders, N.; Krabbe, J.G.; Kool, J.; Niessen, W.M.A.; Orru, R.V.A.; Irth, H.

2008-01-01

An integrated online screening system was developed to rapidly screen homogeneous catalysts for activity toward a selected synthesis. The continuous-flow system comprises standard HPLC pumps for the delivery of substrates, an HPLC autosampler for the injection of homogeneous catalysts, a

Noncontact Atomic Force Microscopy: An Emerging Tool for Fundamental Catalysis Research.

Science.gov (United States)

Altman, Eric I; Baykara, Mehmet Z; Schwarz, Udo D

2015-09-15

Although atomic force microscopy (AFM) was rapidly adopted as a routine surface imaging apparatus after its introduction in 1986, it has not been widely used in catalysis research. The reason is that common AFM operating modes do not provide the atomic resolution required to follow catalytic processes; rather the more complex noncontact (NC) mode is needed. Thus, scanning tunneling microscopy has been the principal tool for atomic scale catalysis research. In this Account, recent developments in NC-AFM will be presented that offer significant advantages for gaining a complete atomic level view of catalysis. The main advantage of NC-AFM is that the image contrast is due to the very short-range chemical forces that are of interest in catalysis. This motivated our development of 3D-AFM, a method that yields quantitative atomic resolution images of the potential energy surfaces that govern how molecules approach, stick, diffuse, and rebound from surfaces. A variation of 3D-AFM allows the determination of forces required to push atoms and molecules on surfaces, from which diffusion barriers and variations in adsorption strength may be obtained. Pushing molecules towards each other provides access to intermolecular interaction between reaction partners. Following reaction, NC-AFM with CO-terminated tips yields textbook images of intramolecular structure that can be used to identify reaction intermediates and products. Because NC-AFM and STM contrast mechanisms are distinct, combining the two methods can produce unique insight. It is demonstrated for surface-oxidized Cu(100) that simultaneous 3D-AFM/STM yields resolution of both the Cu and O atoms. Moreover, atomic defects in the Cu sublattice lead to variations in the reactivity of the neighboring O atoms. It is shown that NC-AFM also allows a straightforward imaging of work function variations which has been used to identify defect charge states on catalytic surfaces and to map charge transfer within an individual

Catalysis of heat-to-work conversion in quantum machines

Science.gov (United States)

Ghosh, A.; Latune, C. L.; Davidovich, L.; Kurizki, G.

2017-11-01

We propose a hitherto-unexplored concept in quantum thermodynamics: catalysis of heat-to-work conversion by quantum nonlinear pumping of the piston mode which extracts work from the machine. This concept is analogous to chemical reaction catalysis: Small energy investment by the catalyst (pump) may yield a large increase in heat-to-work conversion. Since it is powered by thermal baths, the catalyzed machine adheres to the Carnot bound, but may strongly enhance its efficiency and power compared with its noncatalyzed counterparts. This enhancement stems from the increased ability of the squeezed piston to store work. Remarkably, the fraction of piston energy that is convertible into work may then approach unity. The present machine and its counterparts powered by squeezed baths share a common feature: Neither is a genuine heat engine. However, a squeezed pump that catalyzes heat-to-work conversion by small investment of work is much more advantageous than a squeezed bath that simply transduces part of the work invested in its squeezing into work performed by the machine.

Heterobimetallic transition metal/rare earth metal bifunctional catalysis: a Cu/Sm/Schiff base complex for syn-selective catalytic asymmetric nitro-Mannich reaction.

Science.gov (United States)

Handa, Shinya; Gnanadesikan, Vijay; Matsunaga, Shigeki; Shibasaki, Masakatsu

2010-04-07

The full details of a catalytic asymmetric syn-selective nitro-Mannich reaction promoted by heterobimetallic Cu/Sm/dinucleating Schiff base complexes are described, demonstrating the effectiveness of the heterobimetallic transition metal/rare earth metal bifunctional catalysis. The first-generation system prepared from Cu(OAc)(2)/Sm(O-iPr)(3)/Schiff base 1a = 1:1:1 with an achiral phenol additive was partially successful for achieving the syn-selective catalytic asymmetric nitro-Mannich reaction. The substrate scope and limitations of the first-generation system remained problematic. After mechanistic studies on the catalyst prepared from Sm(O-iPr)(3), we reoptimized the catalyst preparation method, and a catalyst derived from Sm(5)O(O-iPr)(13) showed broader substrate generality as well as higher reactivity and stereoselectivity compared to Sm(O-iPr)(3). The optimal system with Sm(5)O(O-iPr)(13) was applicable to various aromatic, heteroaromatic, and isomerizable aliphatic N-Boc imines, giving products in 66-99% ee and syn/anti = >20:1-13:1. Catalytic asymmetric synthesis of nemonapride is also demonstrated using the catalyst derived from Sm(5)O(O-iPr)(13).

Quantifying the limits of transition state theory in enzymatic catalysis.

Science.gov (United States)

Zinovjev, Kirill; Tuñón, Iñaki

2017-11-21

While being one of the most popular reaction rate theories, the applicability of transition state theory to the study of enzymatic reactions has been often challenged. The complex dynamic nature of the protein environment raised the question about the validity of the nonrecrossing hypothesis, a cornerstone in this theory. We present a computational strategy to quantify the error associated to transition state theory from the number of recrossings observed at the equicommittor, which is the best possible dividing surface. Application of a direct multidimensional transition state optimization to the hydride transfer step in human dihydrofolate reductase shows that both the participation of the protein degrees of freedom in the reaction coordinate and the error associated to the nonrecrossing hypothesis are small. Thus, the use of transition state theory, even with simplified reaction coordinates, provides a good theoretical framework for the study of enzymatic catalysis. Copyright © 2017 the Author(s). Published by PNAS.

Faraday Discussions meeting Catalysis for Fuels.

Science.gov (United States)

Fischer, Nico; Kondrat, Simon A; Shozi, Mzamo

2017-05-02

Welcome to Africa was the motto when after more than 100 years the flag ship conference series of the Royal Society of Chemistry, the Faraday Discussions was hosted for the first time on the African Continent. Under the fitting topic 'Catalysis for Fuels' over 120 delegates followed the invitation by the conference chair Prof. Graham Hutchings FRS (Cardiff Catalysis Institute), his organizing committee and the co-organizing DST-NRF Centre of Excellence in Catalysis c*change (). In the presentations of 21 invited speakers and 59 posters, cutting edge research in the field of catalysis for fuels, designing new catalysts for synthetic fuels, hydrocarbon conversion in the production of synthetic fuels and novel photocatalysis was presented over the two-day meeting. The scene was set by the opening lecture of Prof. Enrique Iglesias (UC Berkeley) and wrapped-up with the concluding remarks by Philip Gibson (SASOL).

Catalysis induced by radiations

International Nuclear Information System (INIS)

Jimenez B, J.; Gonzalez J, J. C.

2010-01-01

In Mexico is generated a great quantity of residuals considered as dangerous, for its capacity of corrosion, reactivity, toxicity to the environment, inflammability and biological-infectious potential. It is important to mention that the toxic compounds cannot be discharged to the sewerage systems and much less to the receiving bodies of water. The usual treatment that receives the dangerous residuals is the incineration and the bordering. The incineration is an efficient form of treating the residuals, but it can be dioxins source and benzofurans, being the phenol and chloro phenol the precursors of these compounds. At the present time the radiolytic degradation of organic compounds has been broadly studied, especially the 4-chloro phenol and of same form the photo catalysis of organic compounds. However the combination of both processes, called radio catalysis is barely reported. In this work the results of the experiments realized for to degrade the 4-chloro phenol by means of radio catalysis are reported. (Author)

Reaction of organic ytterbium derivatives with alkyl- and arylhalogenides

International Nuclear Information System (INIS)

Rybakova, L.F.; Syutkina, O.P.; Garbar, A.V.; Petrov, Eh.S.

1988-01-01

Interaction of a series of organic halogenides with organic bivalent ytterbium derivatives (like Grignard reagent, RYbX, where R=CH 3 , C 6 H 5 ; X=Br, I) under metal complex catalysis is studied. Aromatic and aliphatic ytterbium derivatives undergo a reaction of cross combination with organic iodides and bromides under catalysis by NiCl 2 (PPh 3 ) 2 and Pd(PPh 3 ) 4 complexes. Therewith organo-ytterbium compounds quantitatively react with alkyl (aryl) iodides, bromine substitution for iodine in arylhalogenides results in decrease of yield of cross-combination products. Reactions of organo-ytterbium compounds with organic halogenides are more effectively catalysed by nickel complexes than by palladium ones

A New Homogeneous Catalyst for the Dehydrogenation of Dimethylamine Borane Starting with Ruthenium(III Acetylacetonate

Directory of Open Access Journals (Sweden)

Ebru Ünel Barın

2015-06-01

Full Text Available The catalytic activity of ruthenium(III acetylacetonate was investigated for the first time in the dehydrogenation of dimethylamine borane. During catalytic reaction, a new ruthenium(II species is formed in situ from the reduction of ruthenium(III and characterized using UV-Visible, Fourier transform infrared (FTIR, 1H NMR, and mass spectroscopy. The most likely structure suggested for the ruthenium(II species is mer-[Ru(N2Me43(acacH]. Mercury poisoning experiment indicates that the catalytic dehydrogenation of dimethylamine-borane is homogeneous catalysis. The kinetics of the catalytic dehydrogenation of dimethylamine borane starting with Ru(acac3 were studied depending on the catalyst concentration, substrate concentration and temperature. The hydrogen generation was found to be first-order with respect to catalyst concentration and zero-order regarding the substrate concentration. Evaluation of the kinetic data provides the activation parameters for the dehydrogenation reaction: the activation energy Ea = 85 ± 2 kJ·mol−1, the enthalpy of activation ∆H# = 82 ± 2 kJ·mol−1 and the entropy of activation; ∆S# = −85 ± 5 J·mol−1·K−1. The ruthenium(II catalyst formed from the reduction of ruthenium(III acetylacetonate provides 1700 turnovers over 100 hours in hydrogen generation from the dehydrogenation of dimethylamine borane before deactivation at 60 °C.

A Voltammetric Determination of the Rate Constant of a One-Way Homogeneous Chemical Reaction in a System of Two Immiscible Liquid Phases

Czech Academy of Sciences Publication Activity Database

Holub, Karel; Brusová, Zuzana; Štulík, K.; Mareček, Vladimír

2004-01-01

Roč. 574, č. 1 (2004), s. 101-106 ISSN 0022-0728 R&D Projects: GA ČR GA203/03/0822 Institutional research plan: CEZ:AV0Z4040901 Keywords : liquid|liquid interfaces * homogeneous reaction * voltammetry Subject RIV: CG - Electrochemistry Impact factor: 2.228, year: 2004

Chaudhari, Prof. Raghunath Vitthal

Indian Academy of Sciences (India)

Specialization: Homogeneous and Heterogeneous Catalysis, Biomass Conversion; Multiphase Reactors, Chemical Reaction Engineering and Kinetics & Mechanism Address: Deane E Ackers Distinguished Professor, Department of Chemical & Petroleum Engineering, CEBC, The University of Kansas, 1501, Wakarusa Dr ...

Synthesis and characterization of hydrotalcite-hydroxyapatite material doped with carbon nanotubes and its application in catalysis of transesterification reaction

International Nuclear Information System (INIS)

Rodrigues, E.; Barros, T.; Pereira, C.; Almeida, O.; Brasil, H.; Reis, M.A L. dos

2018-01-01

The aim of this study was to synthesize and characterize hydrotalcite-hydroxyapatite (HTHAp) material doped with three different proportions (1, 5 and 15% w/w) of carbon nanotubes (NTC) in order to evaluate its potential as a heterogeneous catalyst in the soybean oil methanolysis reaction. The synthesis of the HTHAp material was performed by the co-precipitation method (10≤pH≤ 11) with ultrasonic homogenization and hydrothermal treatment at 80 °C. XRD, SEM/EDS, FT-IR, Raman, N 2 physisorption and TG/DTA were the characterization techniques performed. The sample HTHAp1NTC, doped at 1% w/w, was tested as a catalyst under two temperature conditions (180 and 240 °C), 4 h reaction time, 2.5% catalyst loading and alcohol:oil ratio of 12:1. Doping contributed to improve structural, morphological and thermal stability properties of HTHAp material. The yield results achieved 35.2% (180 °C) and 40.5% (240 °C) qualifying the HTHAp material doped with CNT as a potential catalyst in the transesterification reaction. (author)

Reactions the private life of atoms

CERN Document Server

Atkins, Peter

2011-01-01

Through an innovative, closely integrated design of images and text, and his characteristically clear, precise, and economical exposition, Peter Atkins explains the processes involved in chemical reactions. He begins by introducing a 'tool kit' of basic reactions, such as precipitation, corrosion, and catalysis, and concludes by showing how these building blocks are brought together in more complex processes such as photosynthesis.

EMSL and Institute for Integrated Catalysis (IIC) Catalysis Workshop

Energy Technology Data Exchange (ETDEWEB)

Campbell, Charles T.; Datye, Abhaya K.; Henkelman, Graeme A.; Lobo, Raul F.; Schneider, William F.; Spicer, Leonard D.; Tysoe, Wilfred T.; Vohs, John M.; Baer, Donald R.; Hoyt, David W.; Thevuthasan, Suntharampillai; Mueller, Karl T.; Wang, Chong M.; Washton, Nancy M.; Lyubinetsky, Igor; Teller, Raymond G.; Andersen, Amity; Govind, Niranjan; Kowalski, Karol; Kabius, Bernd C.; Wang, Hongfei; Campbell, Allison A.; Shelton, William A.; Bylaska, Eric J.; Peden, Charles HF; Wang, Yong; King, David L.; Henderson, Michael A.; Rousseau, Roger J.; Szanyi, Janos; Dohnalek, Zdenek; Mei, Donghai; Garrett, Bruce C.; Ray, Douglas; Futrell, Jean H.; Laskin, Julia; DuBois, Daniel L.; Kuprat, Laura R.; Plata, Charity

2011-05-24

Within the context of significantly accelerating scientific progress in research areas that address important societal problems, a workshop was held in November 2010 at EMSL to identify specific and topically important areas of research and capability needs in catalysis-related science.

Isotopes in heterogeneous catalysis

CERN Document Server

Hargreaves, Justin SJ

2006-01-01

The purpose of this book is to review the current, state-of-the-art application of isotopic methods to the field of heterogeneous catalysis. Isotopic studies are arguably the ultimate technique in in situ methods for heterogeneous catalysis. In this review volume, chapters have been contributed by experts in the field and the coverage includes both the application of specific isotopes - Deuterium, Tritium, Carbon-14, Sulfur-35 and Oxygen-18 - as well as isotopic techniques - determination of surface mobility, steady state transient isotope kinetic analysis, and positron emission profiling.

A novel tandem Betti/Ullmann oxidation reaction as an efficient route ...

Indian Academy of Sciences (India)

Betti reaction; cross-coupling reaction; oxidation; heterogeneous catalysis. Abstract. A novel tandem Betti/Ullmann/oxidation reaction was used for synthesis of new oxazepine derivatives containing kojic acid. This protocol ... This method provides a new and useful strategy for the construction of heterocycles. Also novel Betti ...

Primary Alcohols from Terminal Olefins: Formal Anti-Markovnikov Hydration via Triple Relay Catalysis

KAUST Repository

Dong, G.

2011-09-15

Alcohol synthesis is critical to the chemical and pharmaceutical industries. The addition of water across olefins to form primary alcohols (anti-Markovnikov olefin hydration) would be a broadly useful reaction but has largely proven elusive; an indirect hydroboration/oxidation sequence requiring stoichiometric borane and oxidant is currently the most practical methodology. Here, we report a more direct approach with the use of a triple relay catalysis system that couples palladium-catalyzed oxidation, acid-catalyzed hydrolysis, and ruthenium-catalyzed reduction cycles. Aryl-substituted terminal olefins are converted to primary alcohols by net reaction with water in good yield and excellent regioselectivity.

Homogenization methods for heterogeneous assemblies

International Nuclear Information System (INIS)

Wagner, M.R.

1980-01-01

The third session of the IAEA Technical Committee Meeting is concerned with the problem of homogenization of heterogeneous assemblies. Six papers will be presented on the theory of homogenization and on practical procedures for deriving homogenized group cross sections and diffusion coefficients. That the problem of finding so-called ''equivalent'' diffusion theory parameters for the use in global reactor calculations is of great practical importance. In spite of this, it is fair to say that the present state of the theory of second homogenization is far from being satisfactory. In fact, there is not even a uniquely accepted approach to the problem of deriving equivalent group diffusion parameters. Common agreement exists only about the fact that the conventional flux-weighting technique provides only a first approximation, which might lead to acceptable results in certain cases, but certainly does not guarantee the basic requirement of conservation of reaction rates

Material-Efficient Microfluidic Platform for Exploratory Studies of Visible-Light Photoredox Catalysis.

Science.gov (United States)

Coley, Connor W; Abolhasani, Milad; Lin, Hongkun; Jensen, Klavs F

2017-08-07

We present an automated microfluidic platform for in-flow studies of visible-light photoredox catalysis in liquid or gas-liquid reactions at the 15 μL scale. An oscillatory flow strategy enables a flexible residence time while preserving the mixing and heat transfer advantages of flow systems. The adjustable photon flux made possible with the platform is characterized using actinometry. Case studies of oxidative hydroxylation of phenylboronic acids and dimerization of thiophenol demonstrate the capabilities and advantages of the system. Reaction conditions identified through droplet screening translate directly to continuous synthesis with minor platform modifications. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Homogeneous, heterogeneous and enzymatic catalysis for transesterification of high free fatty acid oil (waste cooking oil) to biodiesel: a review.

Science.gov (United States)

Lam, Man Kee; Lee, Keat Teong; Mohamed, Abdul Rahman

2010-01-01

In the last few years, biodiesel has emerged as one of the most potential renewable energy to replace current petrol-derived diesel. It is a renewable, biodegradable and non-toxic fuel which can be easily produced through transesterification reaction. However, current commercial usage of refined vegetable oils for biodiesel production is impractical and uneconomical due to high feedstock cost and priority as food resources. Low-grade oil, typically waste cooking oil can be a better alternative; however, the high free fatty acids (FFA) content in waste cooking oil has become the main drawback for this potential feedstock. Therefore, this review paper is aimed to give an overview on the current status of biodiesel production and the potential of waste cooking oil as an alternative feedstock. Advantages and limitations of using homogeneous, heterogeneous and enzymatic transesterification on oil with high FFA (mostly waste cooking oil) are discussed in detail. It was found that using heterogeneous acid catalyst and enzyme are the best option to produce biodiesel from oil with high FFA as compared to the current commercial homogeneous base-catalyzed process. However, these heterogeneous acid and enzyme catalyze system still suffers from serious mass transfer limitation problems and therefore are not favorable for industrial application. Nevertheless, towards the end of this review paper, a few latest technological developments that have the potential to overcome the mass transfer limitation problem such as oscillatory flow reactor (OFR), ultrasonication, microwave reactor and co-solvent are reviewed. With proper research focus and development, waste cooking oil can indeed become the next ideal feedstock for biodiesel.

Recent Advances in the Application of Magnetic Nanoparticles as a Support for Homogeneous Catalysts

Science.gov (United States)

Govan, Joseph; Gun’ko, Yurii K.

2014-01-01

Magnetic nanoparticles are a highly valuable substrate for the attachment of homogeneous inorganic and organic containing catalysts. This review deals with the very recent main advances in the development of various nanocatalytic systems by the immobilisation of homogeneous catalysts onto magnetic nanoparticles. We discuss magnetic core shell nanostructures (e.g., silica or polymer coated magnetic nanoparticles) as substrates for catalyst immobilisation. Then we consider magnetic nanoparticles bound to inorganic catalytic mesoporous structures as well as metal organic frameworks. Binding of catalytically active small organic molecules and polymers are also reviewed. After that we briefly deliberate on the binding of enzymes to magnetic nanocomposites and the corresponding enzymatic catalysis. Finally, we draw conclusions and present a future outlook for the further development of new catalytic systems which are immobilised onto magnetic nanoparticles. PMID:28344220

Catalysis as a foundational pillar of green chemistry

Energy Technology Data Exchange (ETDEWEB)

Anastas, Paul T. [White House Office of Science and Technology Policy, Department of Chemistry, University of Nottingham Nottingham, (United Kingdom); Kirchhoff, Mary M. [U.S. Environmental Protection Agency and Trinity College, Washington, DC (United States); Williamson, Tracy C. [U.S. Environmental Protection Agency, Washington, DC (United States)

2001-11-30

are serving as a strong incentive to industry to adopt greener technologies. Developing green chemistry methodologies is a challenge that may be viewed through the framework of the Twelve Principles of Green Chemistry . These principles identify catalysis as one of the most important tools for implementing green chemistry. Catalysis offers numerous green chemistry benefits including lower energy requirements, catalytic versus stoichiometric amounts of materials, increased selectivity, and decreased use of processing and separation agents, and allows for the use of less toxic materials. Heterogeneous catalysis, in particular, addresses the goals of green chemistry by providing the ease of separation of product and catalyst, thereby eliminating the need for separation through distillation or extraction. In addition, environmentally benign catalysts such as clays and zeolites, may replace more hazardous catalysts currently in use. This paper highlights a variety of ways in which catalysis may be used as a pollution prevention tool in green chemistry reactions. The benefits to human health, environment, and the economic goals realized through the use of catalysis in manufacturing and processing are illustrated by focusing on the catalyst design and catalyst applications.

Heterogeneous catalysis in complex, condensed reaction media

Energy Technology Data Exchange (ETDEWEB)

Cantu, David C.; Wang, Yang-Gang; Yoon, Yeohoon; Glezakou, Vassiliki-Alexandra; Rousseau, Roger; Weber, Robert S.

2017-07-01

Many reactions required for the upgrading of biomass into fuels and chemicals—hydrogenation, hydrodeoxygenation, hydrocracking—are ostensibly similar to those practiced in the upgrading of petroleum into fuels. But, repurposing hydroprocessing catalysts from refinery operations to treat bio-oil has proved to be unsatisfactory. New catalysts are needed because the composition of the biogenic reactants differs from that of petroleum-derived feedstocks (e.g. the low concentration of sulfur in cellulose-derived biomass precludes use of metal sulfide catalysts unless sulfur is added to the reaction stream). New processes are needed because bio-oils oligomerize rapidly, forming intractable coke and “gunk”, at temperatures so low that the desired upgrading reactions are impractically slow, and so low that the bio-oil upgrading must be handled as a condensed fluid. Ideally, the new catalysts and processes would exploit the properties of the multiple phases present in condensed bio-oil, notably the polarizability and structure of the fluid near a catalyst’s surface in the cybotactic region. The results of preliminary modeling of the cybotactic region of different catalyst surfaces in the hydrogenation of phenol suggest that Pd catalysts supported on hydrophilic surfaces are more active than catalysts based on lipophilic supports because the former serve to enhance the concentration of the phenol in the vicinity of the Pd. The effect stems from thermodynamics, not the rate of mass transport. This work was supported by the US Department of Energy, Office of Energy Efficiency and Renewable Energy, Bioenergy Technologies Office. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle.

Characterization techniques for graphene-based materials in catalysis

Directory of Open Access Journals (Sweden)

Maocong Hu

2017-06-01

Full Text Available Graphene-based materials have been studied in a wide range of applications including catalysis due to the outstanding electronic, thermal, and mechanical properties. The unprecedented features of graphene-based catalysts, which are believed to be responsible for their superior performance, have been characterized by many techniques. In this article, we comprehensively summarized the characterization methods covering bulk and surface structure analysis, chemisorption ability determination, and reaction mechanism investigation. We reviewed the advantages/disadvantages of different techniques including Raman spectroscopy, X-ray photoelectron spectroscopy (XPS, Fourier transform infrared spectroscopy (FTIR and Diffuse Reflectance Fourier Transform Infrared Spectroscopy (DRIFTS, X-Ray diffraction (XRD, X-ray absorption near edge structure (XANES and X-ray absorption fine structure (XAFS, atomic force microscopy (AFM, scanning electron microscopy (SEM, transmission electron microscopy (TEM, high-resolution transmission electron microscopy (HRTEM, ultraviolet-visible spectroscopy (UV-vis, X-ray fluorescence (XRF, inductively coupled plasma mass spectrometry (ICP, thermogravimetric analysis (TGA, Brunauer–Emmett–Teller (BET, and scanning tunneling microscopy (STM. The application of temperature-programmed reduction (TPR, CO chemisorption, and NH3/CO2-temperature-programmed desorption (TPD was also briefly introduced. Finally, we discussed the challenges and provided possible suggestions on choosing characterization techniques. This review provides key information to catalysis community to adopt suitable characterization techniques for their research.

Editorial: Nanoscience makes catalysis greener

KAUST Repository

Polshettiwar, Vivek

2012-01-09

Green chemistry by nanocatalysis: Catalysis is a strategic field of science because it involves new ways of meeting energy and sustainability challenges. The concept of green chemistry, which makes the science of catalysis even more creative, has become an integral part of sustainability. This special issue is at the interface of green chemistry and nanocatalysis, and features excellent background articles as well as the latest research results. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Kinetic Studies on the Selective Oxidation of Benzyl Alcohols in Organic Medium under Phase Transfer Catalysis

Directory of Open Access Journals (Sweden)

K. Bijudas

2014-07-01

Full Text Available Kinetic studies on the oxidation of benzyl alcohol and substituted benzyl alcohols in benzene as the reaction medium have been studied by using potassium dichromate under phase transfer catalysis (PTC. The phase transfer catalysts (PT catalysts used were tetrabutylammonium bromide (TBAB and tetrabutylphosphonium bromide (TBPB.  Benzyl alcohols were selectively oxidised to corresponding benzaldehydes in good yield (above 90%.  The order of reactivity among the studied benzyl alcohols is p - OCH3 > p - CH3 > - H > p - Cl.  Plots of log k2 versus Hammett's substituent constant (s has been found to be curve shaped and this suggests that there should be a continuous change in transition state with changes in substituent present in the substrate from electron donating to electron withdrawing. A suitable mechanism has been suggested in which the rate determining step involves both C - H bond cleavage and C - O bond formations in concerted manner. © 2014 BCREC UNDIP. All rights reserved.Received: 16th March 2014; Revised: 18th May 2014; Accepted: 18th May 2014[How to Cite: Bijudas, K., Bashpa, P., Nair, T.D.R. (2014. Kinetic Studies on the Selective Oxidation of Benzyl Alcohol and Substituted Benzyl Alcohols in Organic Medium under Phase Transfer Catalysis. Bulletin of Chemical Reaction Engineering & Catalysis, 9 (2: 142-147. (doi:10.9767/bcrec.9.2.6476.142-147][Permalink/DOI: http://dx.doi.org/10.9767/bcrec.9.2.6476.142-147] 

Opportunities for Catalysis in The 21st Century. A report from the Basic Energy Sciences Advisory Committee

Energy Technology Data Exchange (ETDEWEB)

White, J. M.; Bercaw, J.

2002-05-16

Chemical catalysis affects our lives in myriad ways. Catalysis provides a means of changing the rates at which chemical bonds are formed and broken and of controlling the yields of chemical reactions to increase the amounts of desirable products from these reactions and reduce the amounts of undesirable ones. Thus, it lies at the heart of our quality of life: The reduced emissions of modern cars, the abundance of fresh food at our stores, and the new pharmaceuticals that improve our health are made possible by chemical reactions controlled by catalysts. Catalysis is also essential to a healthy economy: The petroleum, chemical, and pharmaceutical industries, contributors of $500 billion to the gross national product of the United States, rely on catalysts to produce everything from fuels to ''wonder drugs'' to paints to cosmetics. Today, our Nation faces a variety of challenges in creating alternative fuels, reducing harmful by-products in manufacturing, cleaning up the environment and preventing future pollution, dealing with the causes of global warming, protecting citizens from the release of toxic substances and infectious agents, and creating safe pharmaceuticals. Catalysts are needed to meet these challenges, but their complexity and diversity demand a revolution in the way catalysts are designed and used. This revolution can become reality through the application of new methods for synthesizing and characterizing molecular and material systems. Opportunities to understand and predict how catalysts work at the atomic scale and the nanoscale are now appearing, made possible by breakthroughs in the last decade in computation, measurement techniques, and imaging and by new developments in catalyst design, synthesis, and evaluation.

Photocatalytic Water-Splitting Reaction from Catalytic and Kinetic Perspectives

KAUST Repository

Hisatomi, Takashi; Takanabe, Kazuhiro; Domen, Kazunari

2014-01-01

Abstract: Some particulate semiconductors loaded with nanoparticulate catalysts exhibit photocatalytic activity for the water-splitting reaction. The photocatalysis is distinct from the thermal catalysis because photocatalysis involves photophysical

supp12a.doc

Indian Academy of Sciences (India)

for. Application of quinoxaline based diimidazolium salt in palladium catalyzed cross-coupling reactions. Mujahuddin M. Siddiqui, Mohammed Waheed, Sajad A. Bhat and Maravanji S. Balakrishna*. Organophosphorus and Homogenous catalysis laboratory, Department of Chemistry, Indian Institute of Technology Bombay, ...

Synthesis of biodiesel from soybean oil by coupling catalysis with subcritical methanol

International Nuclear Information System (INIS)

Yin Jianzhong; Xiao Min; Wang Aiqin; Xiu Zhilong

2008-01-01

Biodiesel synthesis from soybean oil and methanol was investigated under supercritical and subcritical conditions. Under the supercritical conditions, the maximum methyl ester yield exceeded 98% when the molar ratio of methanol to oil was 42:1 and the reaction temperature ranged from 260 deg. C to 350 deg. C. In order to decrease the operational temperature and pressures and to increase the conversion efficiency of methanol, first co-solvent was added to the reaction mixture to improve the reaction process, and then a novel idea was presented in which catalysis and supercritical effect were coupled together. Thus, with 2.5 wt% hexane, temperature of 300 deg. C, methanol to oil ratio of 42, a 85.5% conversion is observed in 30 min, while a 62.2% conversion is observed without hexane in the same condition; with less carbon dioxide, temperature of 300 deg. C, methanol to oil ratio of 42, a 91.6% conversion is observed in 20 min, while a 51.4% conversion is observed without carbon dioxide in the same condition; With only a little amount of potassium hydroxide as the catalyst (KOH/oil = 0.1 wt%), a 98% yield of methyl esters was obtained in 10 min at a reaction temperature of 160 deg. C and the molar ratio (methanol/oil) of 24:1. In contrast, above 1 wt% of catalyst is required in the conventional alkali-catalyzed method; while only 6% yield of methyl ester was obtained at 260 deg. C (corresponding to subcritical conditions) without the catalyst. This result demonstrated that by coupling the catalysis and subcritical operation, the amount of catalyst could be largely reduced and the methanol utilization could be significantly enhanced. Thus, the present method offers some advantages over both the conventional alkali-catalyst method and the expensive supercritical method

Nano catalysis: Academic Discipline and Industrial Realities

International Nuclear Information System (INIS)

Olveira, S.; Forster, S.P.; Seeger, S.

2014-01-01

Nano technology plays a central role in both academic research and industrial applications. Nano enabled products are not only found in consumer markets, but also importantly in business to business markets (B2B). One of the oldest application areas of nano technology is nano catalysis—an excellent example for such a B2 B market. Several existing reviews illustrate the scientific developments in the field of nano catalysis. The goal of the present review is to provide an up-to-date picture of academic research and to extend this picture by an industrial and economic perspective. We therefore conducted an extensive search on several scientific databases and we further analyzed more than 1,500 nano catalysis-related patents and numerous market studies. We found that scientists today are able to prepare nano catalysts with superior characteristics regarding activity, selectivity, durability, and recoverability, which will contribute to solve current environmental, social, and industrial problems. In industry, the potential of nano catalysis is recognized, clearly reflected by the increasing number of nano catalysis-related patents and products on the market. The current nano catalysis research in academic and industrial laboratories will therefore enable a wealth of future applications in the industry

Operando research in heterogeneous catalysis

CERN Document Server

Groot, Irene

2017-01-01

This book is devoted to the emerging field of techniques for visualizing atomic-scale properties of active catalysts under actual working conditions, i.e. high gas pressures and high temperatures. It explains how to understand these observations in terms of the surface structures and dynamics and their detailed interplay with the gas phase. This provides an important new link between fundamental surface physics and chemistry, and applied catalysis. The book explains the motivation and the necessity of operando studies, and positions these with respect to the more traditional low-pressure investigations on the one hand and the reality of industrial catalysis on the other. The last decade has witnessed a rapid development of new experimental and theoretical tools for operando studies of heterogeneous catalysis. The book has a strong emphasis on the new techniques and illustrates how the challenges introduced by the harsh, operando conditions are faced for each of these new tools. Therefore, one can also read th...

First Principles Molecular Dynamics Study of Catalysis for Polyolefins: the Ziegler-Natta Heterogeneous System.

Directory of Open Access Journals (Sweden)

Michele Parrinello

2002-04-01

Full Text Available Abstract: We review part of our recent ab initio molecular dynamics study on the Ti-based Ziegler-Natta supported heterogeneous catalysis of α-olefins. The results for the insertion of ethylene in the metal-carbon bond are discussed as a fundamental textbook example of polymerization processes. Comparison with the few experimental data available has shown that simulation can reproduce activation barriers and the overall energetics of the reaction with sufficient accuracy. This puts these quantum dynamical simulations in a new perspective as a virtual laboratory where the microscopic picture of the catalysis, which represents an important issue that still escapes experimental probes, can be observed and understood. These results are then discussed in comparison with a V-based catalyst in order to figure out analogies and differences with respect to the industrially more successful Tibased systems.

Organic synthesis via magnetic attraction: benign and sustainable protocols using magnetic nanoferrites

Science.gov (United States)

Magnetic nano-catalysts have been prepared using simple modification of iron ferrites wherein their quasi-homogeneous state, because of nm size range, facilitates the catalysis process as increased surface is available for reaction; the easy separation of the catalysts by externa...

Journal of Chemical Sciences | Indian Academy of Sciences

Indian Academy of Sciences (India)

(±)Methanodibenzodiazocine tethered [C-H]+ functional site: Study towards benzoin condensation and Baylis-Hillman reactions ... Tröger's base; Imidazolium salt; N-Heterocyclic carbenes; C-H bond activation. ... The possible applications of these newly prepared salts were investigated in homogeneous catalysis.

Advancing Sustainable Catalysis with Magnetite Surface ...

Science.gov (United States)

This article surveys the recent developments in the synthesis, surface modification, and synthetic applications of magnetitenanoparticles. The emergence of iron(II,III) oxide (triiron tetraoxide or magnetite; Fe3O4, or FeO•Fe2O3) nanoparticles as a sustainable support in heterogeneous catalysis is highlighted. Use of an oxide of earth-abundant iron for various applications in catalysis and environmental remediation.

Keynotes in energy-related catalysis

CERN Document Server

Kaliaguine, S

2011-01-01

Catalysis by solid acids, which includes (modified) zeolites, is of special relevance to energy applications. Acid catalysis is highly important in modern petroleum refining operations - large-scale processes such as fluid catalytic cracking, catalytic reforming, alkylation and olefin oligomerization rely on the transformation of hydrocarbons by acid catalysts. (Modified) zeolites are therefore essential for the improvement of existing processes and for technical innovations in the conversion of crude. There can be little doubt that zeolite-based catalysts will play a major role in the futu

Metal- and Ligand-Accelerated Catalysis of the Baylis-Hillman Reaction.

Science.gov (United States)

Aggarwal, Varinder K.; Mereu, Andrea; Tarver, Gary J.; McCague, Ray

1998-10-16

The Baylis-Hillman reaction, the coupling of an unsaturated carbonyl compound/nitrile with aldehydes, is a valuable reaction but is limited in its practicality by poor reaction rates. We have endeavored to accelerate the reaction using Lewis acids and found that while conventional Lewis acids gave reduced rates group III, and lanthanide triflates (5 mol %) gave increased rates. The optimum metal salts were La(OTf)(3) and Sm(OTf)(3), which gave rate accelerations (k(rel)) of approximately 4.7 and 4.9, respectively, in reactions between tert-butyl acrylate and benzaldehyde when using stoichiometric amounts of DABCO. At low loadings of DABCO (up to 10 mol %), no reaction occurred due to association of DABCO with the metal. Use of additional ligands to displace the DABCO from the metal was studied, and the rate of reaction was found to increase further in most cases. Of the ligands tested, at 5 mol %, (+)-binol gave one of the largest rate accelerations (3.4-fold) and was studied in more detail. It was found that reactions occurred even at low DABCO concentration so that here the Lewis base and Lewis acid were able to promote the reaction without interference from each other. While the (+)-binol (and other chiral ligands) failed to provide any significant asymmetric induction, a substantial nonlinear effect was observed with binol. Thus, use of racemic binol gave no effect on the rate. In seeking to maximize the rate attainable, more soluble (liquid) ligands were studied. Diethyl tartrate and triethanolamine gave rate enhancements of 5.2x and 3.5x at 50 mol %, respectively, versus 1.5x and 2.3x at 5 mol %. The best protocol was to use 100 mol % DABCO, 50 mol % triethanolamine, and 5 mol % La(OTf)(3). This gave overall rate accelerations of between 23-fold and 40-fold depending on the acrylate and approximately 5-fold for acrylonitrile. A simple acid wash removed the reagents, leaving the product in the organic phase. While triethanolamine accelerated the reaction

Metal-organic cooperative catalysis in C-H and C-C bond activation and its concurrent recovery.

Science.gov (United States)

Park, Young Jun; Park, Jung-Woo; Jun, Chul-Ho

2008-02-01

The development of an efficient catalytic activation (cleavage) system for C-H and C-C bonds is an important challenge in organic synthesis, because these bonds comprise a variety of organic molecules such as natural products, petroleum oils, and polymers on the earth. Among many elegant approaches utilizing transition metals to activate C-H and C-C bonds facilely, chelation-assisted protocols based on the coordinating ability of an organic moiety have attracted great attention, though they have often suffered from the need for an intact coordinating group in a substrate. In this Account, we describe our entire efforts to activate C-H or C-C bonds adjacent to carbonyl groups by employing a new concept of metal-organic cooperative catalysis (MOCC), which enables the temporal installation of a 2-aminopyridyl group into common aldehydes or ketones in a catalytic way. Consequently, a series of new catalytic reactions such as alcohol hydroacylation, oxo-ester synthesis, C-C triple bond cleavage, hydrative dimerization of alkynes, and skeletal rearrangements of cyclic ketones was realized through MOCC. In particular, in the quest for an optimized MOCC system composed of a Wilkinson's catalyst (Ph 3P) 3RhCl and an organic catalyst (2-amino-3-picoline), surprising efficiency enhancements could be achieved when benzoic acid and aniline were introduced as promoters for the aldimine formation process. Furthermore, a notable accomplishment of C-C bond activation has been made using 2-amino-3-picoline as a temporary chelating auxiliary in the reactions of unstrained ketones with various terminal olefins and Wilkinson's catalyst. In the case of seven-membered cyclic ketones, an interesting ring contraction to five- or six-membered ones takes place through skeletal rearrangements initiated by the C-C bond activation of MOCC. On the other hand, the fundamental advances of these catalytic systems into recyclable processes could be achieved by immobilizing both metal and organic

Synergistic Diazo-OH Insertion/Conia-Ene Cascade Catalysis for the Stereoselective Synthesis of γ-Butyrolactones and Tetrahydrofurans.

Science.gov (United States)

Hunter, Arianne C; Schlitzer, Steven C; Sharma, Indrajeet

2016-11-02

A novel and highly efficient diazo-OH insertion/Conia-ene cascade reaction of readily available homopropargylic acids and alcohols with diazo carbonyl compounds is described. The cascade reaction involves a synergistic Rh/Ag/Au catalyst cocktail and proceeds instantly with a variety of substituted diazo compounds and acids/alcohols to provide functionalized γ-butyrolactones and tetrahydrofurans with complete regio- and stereoselectivity. The unprecedented rate-enhancement, complete stereoselectivity, and the enabling of new Conia-ene cyclizations suggest a concerted [4+1]-cycloaddition reaction pathway under synergistic (Rh/Ag/Au)-catalysis conditions. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Heterogeneous Catalysis: Deuterium Exchange Reactions of Hydrogen and Methane

Science.gov (United States)

Mirich, Anne; Miller, Trisha Hoette; Klotz, Elsbeth; Mattson, Bruce

2015-01-01

Two gas phase deuterium/hydrogen exchange reactions are described utilizing a simple inexpensive glass catalyst tube containing 0.5% Pd on alumina through which gas mixtures can be passed and products collected for analysis. The first of these exchange reactions involves H[subscript 2] + D[subscript 2], which proceeds at temperatures as low as 77…

Multi-scale simulation of reaction-diffusion systems

NARCIS (Netherlands)

Vijaykumar, A.

2017-01-01

In many reaction-diffusion processes, ranging from biochemical networks, catalysis, to complex self-assembly, the spatial distribution of the reactants and the stochastic character of their interactions are crucial for the macroscopic behavior. The recently developed mesoscopic Green’s Function

[Prediction of common buffer catalysis in hydrolysis of fenchlorazole-ethyl].

Science.gov (United States)

Lin, Jing; Chen, Jing-wen; Zhang, Si-yu; Cai, Xi-yun; Qiao, Xian-liang

2008-09-01

The purpose of this study was to elucidate the effects of temperatures, pH levels and buffer catalysis on the hydrolysis of FCE. The hydrolysis of FCE follows first-order kinetics at different pH levels and temperatures. FCE hydrolysis rates are greatly increased at elevated pH levels and temperatures. The maximum contribution of buffer catalysis to the hydrolysis of FCE was assessed based on application of the Bronsted equations for general acid-base catalysis. The results suggest that the buffer solutions play an obvious catalysis role in hydrolysis of FCE and the hydrolysis rates of FCE are quickened by the buffer solutions. Besides, the buffer catalysis capacity of different buffer solutions is diverse, and the buffer catalysis capacity at different pH levels with the same buffer solutions is different, too. The phosphate buffer at pH = 7 shows the maximal buffer catalysis capacity. The hydrolysis rate constants of FCE as a function of temperature and pH, which were remedied by the buffer catalysis factor, were mathematically combined to predict the hydrolytic dissipation of FCE. The equation suggests that the hydrolysis half-lives of FCE ranged from 7 d to 790 d. Hydrolysis metabolites of FCE were identified by liquid chromatography-mass spectrometry. In basic conditions (pH 8-10), fenchlorazole was formed via breakdown of the ester bond of the safener.

Charge Transfer and Catalysis at the Metal Support Interface

Energy Technology Data Exchange (ETDEWEB)

Baker, Lawrence Robert [Univ. of California, Berkeley, CA (United States)

2012-07-31

Kinetic, electronic, and spectroscopic characterization of model Pt–support systems are used to demonstrate the relationship between charge transfer and catalytic activity and selectivity. The results show that charge flow controls the activity and selectivity of supported metal catalysts. This dissertation builds on extensive existing knowledge of metal–support interactions in heterogeneous catalysis. The results show the prominent role of charge transfer at catalytic interfaces to determine catalytic activity and selectivity. Further, this research demonstrates the possibility of selectively driving catalytic chemistry by controlling charge flow and presents solid-state devices and doped supports as novel methods for obtaining electronic control over catalytic reaction kinetics.

Controllable Catalysis with Nanoparticles: Bimetallic Alloy Systems and Surface Adsorbates

KAUST Repository

Chen, Tianyou

2016-05-16

Transition metal nanoparticles are privileged materials in catalysis due to their high specific surface areas and abundance of active catalytic sites. While many of these catalysts are quite useful, we are only beginning to understand the underlying catalytic mechanisms. Opening the “black box” of nanoparticle catalysis is essential to achieve the ultimate goal of catalysis by design. In this Perspective we highlight recent work addressing the topic of controlled catalysis with bimetallic alloy and “designer” adsorbate-stabilized metal nanoparticles.

Controllable Catalysis with Nanoparticles: Bimetallic Alloy Systems and Surface Adsorbates

KAUST Repository

Chen, Tianyou; Rodionov, Valentin

2016-01-01

Transition metal nanoparticles are privileged materials in catalysis due to their high specific surface areas and abundance of active catalytic sites. While many of these catalysts are quite useful, we are only beginning to understand the underlying catalytic mechanisms. Opening the “black box” of nanoparticle catalysis is essential to achieve the ultimate goal of catalysis by design. In this Perspective we highlight recent work addressing the topic of controlled catalysis with bimetallic alloy and “designer” adsorbate-stabilized metal nanoparticles.

Multi-Scale Computational Enzymology: Enhancing Our Understanding of Enzymatic Catalysis

Science.gov (United States)

Gherib, Rami; Dokainish, Hisham M.; Gauld, James W.

2014-01-01

Elucidating the origin of enzymatic catalysis stands as one the great challenges of contemporary biochemistry and biophysics. The recent emergence of computational enzymology has enhanced our atomistic-level description of biocatalysis as well the kinetic and thermodynamic properties of their mechanisms. There exists a diversity of computational methods allowing the investigation of specific enzymatic properties. Small or large density functional theory models allow the comparison of a plethora of mechanistic reactive species and divergent catalytic pathways. Molecular docking can model different substrate conformations embedded within enzyme active sites and determine those with optimal binding affinities. Molecular dynamics simulations provide insights into the dynamics and roles of active site components as well as the interactions between substrate and enzymes. Hybrid quantum mechanical/molecular mechanical (QM/MM) can model reactions in active sites while considering steric and electrostatic contributions provided by the surrounding environment. Using previous studies done within our group, on OvoA, EgtB, ThrRS, LuxS and MsrA enzymatic systems, we will review how these methods can be used either independently or cooperatively to get insights into enzymatic catalysis. PMID:24384841

Multi-Scale Computational Enzymology: Enhancing Our Understanding of Enzymatic Catalysis

Directory of Open Access Journals (Sweden)

Rami Gherib

2013-12-01

Full Text Available Elucidating the origin of enzymatic catalysis stands as one the great challenges of contemporary biochemistry and biophysics. The recent emergence of computational enzymology has enhanced our atomistic-level description of biocatalysis as well the kinetic and thermodynamic properties of their mechanisms. There exists a diversity of computational methods allowing the investigation of specific enzymatic properties. Small or large density functional theory models allow the comparison of a plethora of mechanistic reactive species and divergent catalytic pathways. Molecular docking can model different substrate conformations embedded within enzyme active sites and determine those with optimal binding affinities. Molecular dynamics simulations provide insights into the dynamics and roles of active site components as well as the interactions between substrate and enzymes. Hybrid quantum mechanical/molecular mechanical (QM/MM can model reactions in active sites while considering steric and electrostatic contributions provided by the surrounding environment. Using previous studies done within our group, on OvoA, EgtB, ThrRS, LuxS and MsrA enzymatic systems, we will review how these methods can be used either independently or cooperatively to get insights into enzymatic catalysis.

Catalysis and sustainable (green) chemistry

Energy Technology Data Exchange (ETDEWEB)

Centi, Gabriele; Perathoner, Siglinda [Dipartimento di Chimica Industriale ed Ingegneria dei Materiali, University of Messina, Salita Sperone 31, 98166 Messina (Italy)

2003-01-15

Catalysis is a key technology to achieve the objectives of sustainable (green) chemistry. After introducing the concepts of sustainable (green) chemistry and a brief assessment of new sustainable chemical technologies, the relationship between catalysis and sustainable (green) chemistry is discussed and illustrated via an analysis of some selected and relevant examples. Emphasis is also given to the concept of catalytic technologies for scaling-down chemical processes, in order to develop sustainable production processes which reduce the impact on the environment to an acceptable level that allows self-depuration processes of the living environment.

Scale-up of heterogeneous catalytic reactions

Energy Technology Data Exchange (ETDEWEB)

Heggs, P; Sunderland, P

1979-12-01

This report on the Institution of Chemical Engineers ''Problems in Applied Catalysis'' Meeting (Bath, U.K. 1/4-5/78) covers papers on the nature of the catalyst surface, including the use of IR spectroscopy, electron energy loss spectroscopy, low-energy electron diffraction, electron spectroscopy, secondary ion mass spectroscopy, and modular-beam scattering for investigating solid surfaces and their relevance to catalysis; study of the reaction mechanisms by which catalysis takes place; use of mechanistic models to determine the true chemical kinetics illustrated for the oxidation of benzene to maleic anhydride over a vanadium pentoxide/molybdenum trioxide catalyst; the study with respect to the importance of transport effects in catalyst pellets on scale-up, falsification of true kinetics, and the design of laboratory reactors; full-scale reactor design of packed-bed reactors; and practical scale-up problems illustrated for methanol synthesis over a copper catalyst, ammonia oxidation over a cobalt oxide catalyst, and the steam reforming of naphtha.

Photothermal-enhanced catalysis in core-shell plasmonic hierarchical Cu7S4 microsphere@zeolitic imidazole framework-8.

Science.gov (United States)

Wang, Feifan; Huang, Yanjie; Chai, Zhigang; Zeng, Min; Li, Qi; Wang, Yuan; Xu, Dongsheng

2016-12-01

Conventional semiconductor photocatalysis based on band-edge absorption remains inefficient due to the limited harvesting of solar irradiation and the complicated surface/interface chemistry. Herein, novel photothermal-enhanced catalysis was achieved in a core-shell hierarchical Cu 7 S 4 nano-heater@ZIF-8 heterostructures via near-infrared localized surface plasmon resonance. Our results demonstrated that both the high surface temperature of the photothermal Cu 7 S 4 core and the close-adjacency of catalytic ZIF-8 shell contributed to the extremely enhanced catalytic activity. Under laser irradiation (1450 nm, 500 mW), the cyclocondensation reaction rate increased 4.5-5.4 fold compared to that of the process at room temperature, in which the 1.6-1.8 fold enhancement was due to the localized heating effect. The simulated sunlight experiments showed a photothermal activation efficiency (PTAE) of 0.07%, further indicating the validity of photothermal catalysis based on the plasmonic semiconductor nanomaterials. More generally, this approach provides a platform to improve reaction activity with efficient utilization of solar energy, which can be readily extended to other green-chemistry processes.

New developments in oxidation catalysis

Energy Technology Data Exchange (ETDEWEB)

Rosowski, F. [BASF SE, Ludwigshafen (Germany)

2011-07-01

The impact of heterogeneous catalysis on the economy can be depicted by the global revenue of the chemical industry in 2006, which accounted for 2200 billion Euros with a share of all chemical products produced applying heterogeneous catalysis of about two thirds. [1] The range of products is enormous and they contribute greatly to the quality of our lifes. The advancement in the development of basic and intermediate chemical products is crucially dependent on either the further development of existing catalyst systems or the development of new catalysts and key to success for the chemical industry. Within the context of oxidation catalysis, the following driving forces are guiding research activities: There is a continuous desire to increase the selectivity of a given process in response to both economic as well as ecological needs and taking advantage of higher efficiencies in terms of cost savings and a better utilization of raw materials. A second motivation focuses on raw material change to all abundant and competitive feedstocks requiring both new developments in catalyst design as well as process technology. A more recent motivation refers to the use of metal oxide redox systems which are key to success for the development of novel technologies allowing for the separation of carbon dioxide and the use of carbon dioxide as a feedstock molecule as well as storing renewable energy in a chemical. To date, general ab initio approaches are known for the design of novel catalytic materials only for a few chemical reactions, whereas most industrial catalytic processes have been developed by empirical methods. [2] The development of catalytic materials are either based on the targeted synthesis of catalytic lead structures as well as high throughput methods that allow for the screening of a large range of parameters. [3 - 5] The successful development of catalysts together with reactor technology has led to both significant savings in raw materials and emissions. The

Enzyme catalysis captured using multiple structures from one crystal at varying temperatures

Directory of Open Access Journals (Sweden)

Sam Horrell

2018-05-01

Full Text Available High-resolution crystal structures of enzymes in relevant redox states have transformed our understanding of enzyme catalysis. Recent developments have demonstrated that X-rays can be used, via the generation of solvated electrons, to drive reactions in crystals at cryogenic temperatures (100 K to generate `structural movies' of enzyme reactions. However, a serious limitation at these temperatures is that protein conformational motion can be significantly supressed. Here, the recently developed MSOX (multiple serial structures from one crystal approach has been applied to nitrite-bound copper nitrite reductase at room temperature and at 190 K, close to the glass transition. During both series of multiple structures, nitrite was initially observed in a `top-hat' geometry, which was rapidly transformed to a `side-on' configuration before conversion to side-on NO, followed by dissociation of NO and substitution by water to reform the resting state. Density functional theory calculations indicate that the top-hat orientation corresponds to the oxidized type 2 copper site, while the side-on orientation is consistent with the reduced state. It is demonstrated that substrate-to-product conversion within the crystal occurs at a lower radiation dose at 190 K, allowing more of the enzyme catalytic cycle to be captured at high resolution than in the previous 100 K experiment. At room temperature the reaction was very rapid, but it remained possible to generate and characterize several structural states. These experiments open up the possibility of obtaining MSOX structural movies at multiple temperatures (MSOX-VT, providing an unparallelled level of structural information during catalysis for redox enzymes.

MHD Convective Flow of Jeffrey Fluid Due to a Curved Stretching Surface with Homogeneous-Heterogeneous Reactions.

Directory of Open Access Journals (Sweden)

Maria Imtiaz

Full Text Available This paper looks at the flow of Jeffrey fluid due to a curved stretching sheet. Effect of homogeneous-heterogeneous reactions is considered. An electrically conducting fluid in the presence of applied magnetic field is considered. Convective boundary conditions model the heat transfer analysis. Transformation method reduces the governing nonlinear partial differential equations into the ordinary differential equations. Convergence of the obtained series solutions is explicitly discussed. Characteristics of sundry parameters on the velocity, temperature and concentration profiles are analyzed by plotting graphs. Computations for pressure, skin friction coefficient and surface heat transfer rate are presented and examined. It is noted that fluid velocity and temperature through curvature parameter are enhanced. Increasing values of Biot number correspond to the enhancement in temperature and Nusselt number.

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.

The effect of hot electrons and surface plasmons on heterogeneous catalysis

International Nuclear Information System (INIS)

Kim, Sun Mi; Lee, Si Woo; Moon, Song Yi; Park, Jeong Young

2016-01-01

Hot electrons and surface-plasmon-driven chemistry are amongst the most actively studied research subjects because they are deeply associated with energy dissipation and the conversion processes at the surface and interfaces, which are still open questions and key issues in the surface science community. In this topical review, we give an overview of the concept of hot electrons or surface-plasmon-mediated hot electrons generated under various structural schemes (i.e. metals, metal–semiconductor, and metal–insulator–metal) and their role affecting catalytic activity in chemical reactions. We highlight recent studies on the relation between hot electrons and catalytic activity on metallic surfaces. We discuss possible mechanisms for how hot electrons participate in chemical reactions. We also introduce controlled chemistry to describe specific pathways for selectivity control in catalysis on metal nanoparticles. (topical review)

Noble metal-catalyzed homogeneous and heterogeneous processes in treating simulated nuclear waste media with formic acid

International Nuclear Information System (INIS)

King, R.B.; Bhattacharyya, N.K.; Smith, H.D.

1995-09-01

Simulants for the Hanford Waste Vitrification Plant feed containing the major non-radioactive components Al, Cd, Fe, Mn, Nd, Ni, Si, Zr, Na, CO 3 2 -, NO 3 -, and NO 2 - were used to study reactions of formic acid at 90 degrees C catalyzed by the noble metals Ru, Rh, and/or Pd found in significant quantities in uranium fission products. Such reactions were monitored using gas chromatography to analyze the CO 2 , H 2 , NO, and N 2 O in the gas phase and a microammonia electrode to analyze the NH 4 +/NH 3 in the liquid phase as a function of time. The following reactions have been studied in these systems since they are undesirable side reactions in nuclear waste processing: (1) Decomposition of formic acid to CO 2 + H 2 is undesirable because of the potential fire and explosion hazard of H 2 . Rhodium, which was introduced as soluble RhCl 3 -3H 2 O, was found to be the most active catalyst for H 2 generation from formic acid above ∼ 80 degrees C in the presence of nitrite ion. The H 2 production rate has an approximate pseudo first-order dependence on the Rh concentration, (2) Generation of NH 3 from the formic acid reduction of nitrate and/or nitrite is undesirable because of a possible explosion hazard from NH 4 NO 3 accumulation in a waste processing plant off-gas system. The Rh-catalyzed reduction of nitrogen-oxygen compounds to ammonia by formic acid was found to exhibit the following features: (a) Nitrate rather than nitrite is the principal source of NH 3 . (b) Ammonia production occurs at the expense of hydrogen production. (c) Supported rhodium metal catalysts are more active than rhodium in any other form, suggesting that ammonia production involves heterogeneous rather than homogeneous catalysis

Photocatalytic Water-Splitting Reaction from Catalytic and Kinetic Perspectives

KAUST Repository

Hisatomi, Takashi

2014-10-16

Abstract: Some particulate semiconductors loaded with nanoparticulate catalysts exhibit photocatalytic activity for the water-splitting reaction. The photocatalysis is distinct from the thermal catalysis because photocatalysis involves photophysical processes in particulate semiconductors. This review article presents a brief introduction to photocatalysis, followed by kinetic aspects of the photocatalytic water-splitting reaction.Graphical Abstract: [Figure not available: see fulltext.

Adaptação de forno de microondas doméstico para realização de reações de transesterificação sob refluxo e catálise por argilas Adapting a domestic microwave oven transesterification reactions for under reflux and clay catalysis

Directory of Open Access Journals (Sweden)

Fernando de C. da Silva

2006-04-01

Full Text Available The microwave oven became an important source of heating for many laboratory procedures including accelerating organic reactions. Reactions that require long reflux times can sometimes be carried out in a few hours or minutes in a conventional microwave oven. However, longer reflux times can be troublesome since domestic microwave ovens are not prepared for these harsh conditions. This technical note presents our finding on heterogeneous catalysis transesterification reactions between b-keto-esters and carbohydrate derivatives under heating or microwave irradiation using an adapted domestic microwave oven.

Numerical simulation for aspects of homogeneous and heterogeneous reactions in forced convection flow of nanofluid

Science.gov (United States)

Hayat, Tasawar; Shah, Faisal; Khan, Muhammad Ijaz; Alsaedi, Ahmed

2018-03-01

Mixed convection stagnation point flow of nanofluid by a vertical permeable circular cylinder has been addressed. Water is treated as ordinary liquid while nanoparticles include aluminium oxide, copper and titanium dioxide. Homogeneous-heterogeneous reactions are considered. The nonlinear higher order expressions are changed into first ordinary differential equations and then solved by built-in-Shooting method in mathematica. The results of velocity, temperature, concentration, skin friction and local Nusselt number are discussed. Our results demonstrate that surface drag force and heat transfer rate are enhanced linearly for higher estimation of curvature parameter. Further surface drag force decays for aluminium oxide and it enhances for copper nanoparticle. Heat transfer rate enhances with increasing all three types of nanoparticles. In addition, the lowest heat transfer rate is obtained in case of titanium dioxide when compared with copper and aluminium oxide.

Fuel cells cathode with multiple catalysis and electrocapillary convection; Catodo de celula a combustivel com catalise multipla e conveccao eletrocapilar

Energy Technology Data Exchange (ETDEWEB)

Bambace, Luis Antonio Waack; Nishimori, Miriam; Ramos, Fernando Manuel [Instituto Nacional de Pesquisas Espaciais (INPE), Sao Jose dos Campos, SP (Brazil)], e-mail: bambace@dem.inpe.br; Bastos Netto, Demetrio [Instituto Nacional de Pesquisas Espaciais (INPE), Cachoeira Paulista, SP (Brazil)

2004-07-01

This paper discusses a mathematical model for the chemical reactions and liquid phase flow processes occurring in a fuel cell cathode through non homogeneous catalysis carried by gold and Prussian Blue. The gold is applied inside the porous walls of micro-tubes, which may be obtained through several methods. The wall porosity ranging from 7 to 30% ensures gas exchange between the interior of a micro-tube and its exterior where gas flow takes place. The Prussian Blue consists of a thin porous layer located between the selective membrane and the micro-tube system, with void fraction in the 70 to 80% range. A porous electricity conducting carbide flux collector is placed between the tube system and the bipolar plates. The system return tubes possess a diameter much larger than one of the micro-tubes. The electric potential differences generated by the ionic currents in the system and its asymmetrical shape are used to generate electrocapillary flows, which are related with the surface tension changes with local potential. The hydrogen peroxide concentration and its transport to the Prussian Blue layer, and the oxygen transport inside the reactive tubular system are analyzed in this work. (author)

Microbial electro-catalysis in fuel cell

International Nuclear Information System (INIS)

Dumas, Claire

2007-01-01

Microbial fuel cells (MFC) are devices that ensure the direct conversion of organic matter into electricity using bacterial bio-films as the catalysts of the electrochemical reactions. This study aims at improving the comprehension of the mechanisms involved in electron transfer pathways between the adhered bacteria and the electrodes. This optimization of the MFC power output could be done, for example, in exploring and characterizing various electrode materials. The electrolysis experiments carried out on Geobacter sulfurreducens deal with the microbial catalysis of the acetate oxidation, on the one hand, and the catalysis of the fumarate reduction on the other hand. On the anodic side, differences in current densities appeared on graphite, DSA R and stainless steel (8 A/m 2 , 5 A/m 2 and 0.7 A/m 2 respectively). These variations were explained more by materials roughness differences rather than their nature. Impedance spectroscopy study shows that the electro-active bio-film developed on stainless steel does not seem to modify the evolution of the stainless steel oxide layer, only the imposed potential remains determining. On the cathodic side, stainless steel sustained current densities more than twenty times higher than those obtained with graphite electrodes. The adhesion study of G. sulfurreducens on various materials in a flow cell, suggests that the bio-films resist to the hydrodynamic constraints and are not detached under a shear stress threshold value. The installation of two MFC prototypes, one in a sea station and the other directly in Genoa harbour (Italy) confirms some results obtained in laboratory and were promising for a MFC scale-up. (author) [fr

Reaction mechanism of oxidation, hydroxylation, and epoxidation by hypofluorous acid: A theoretical study of unusual H-bond-assisted catalysis

Czech Academy of Sciences Publication Activity Database

Srnec, Martin; Ončák, Milan; Zahradník, Rudolf

2008-01-01

Roč. 112, č. 6 (2008), s. 3631-3637 ISSN 1089-5639 Institutional research plan: CEZ:AV0Z40550506; CEZ:AV0Z40400503 Keywords : hypofluorous acid * self-catalysis * Rozen oxidation Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.871, year: 2008

Continuous proline catalysis via leaching of solid proline

Directory of Open Access Journals (Sweden)

Suzanne M. Opalka

2011-12-01

Full Text Available Herein, we demonstrate that a homogeneous catalyst can be prepared continuously via reaction with a packed-bed of a catalyst precursor. Specifically, we perform continuous proline catalyzed α-aminoxylations using a packed-bed of L-proline. The system relies on a multistep sequence in which an aldehyde and thiourea additive are passed through a column of solid proline, presumably forming a soluble oxazolidinone intermediate. This transports a catalytic amount of proline from the packed-bed into the reactor coil for subsequent combination with a solution of nitrosobenzene, affording the desired optically active α-aminooxy alcohol after reduction. To our knowledge, this is the first example in which a homogeneous catalyst is produced continuously using a packed-bed. We predict that the method will not only be useful for other L-proline catalyzed reactions, but we also foresee that it could be used to produce other catalytic species in flow.

Advances in catalysis

International Nuclear Information System (INIS)

Eley, D.D.; Pine, H.; Weisz, P.B.

1989-01-01

This book reports on the current state of knowledge concerning structure and catalysis of metals and metal oxide particles, old and new. It addresses the basic and broad problems of what the catalytically relevant surface structures of metals are, where we stand in techniques capable of attacking this problem, and what the current state of knowledge is. The focus is on long-standing, important, and central problem of general investigative methodology and strategy: the pressure gap is created by the fact that the best techniques of surface analysis require high-vacuum conditions, while useful catalysis is confined to conditions of near ambient or higher pressures. The authors review the basic question of the influence of particle size on catalytic behavior of metal particles which involves questions of the basic sciences as much as practical considerations of catalyst design and use. They discuss preparatory techniques, analytical technology, and methods of characterization of these materials

Preparation of Biofuel from Palm Oil Catalyzed by Ammonium Molybdate in Homogeneous Phase

Directory of Open Access Journals (Sweden)

Sepehr Sadighi

2017-04-01

Full Text Available Producing transportation fuels from bio sources was of prime importance due to the strict environmental legislations for producing clean fuels from conventional oil resources. However, the economical impacts of the biofuel production should be considered. In this study, the production of bio-naphtha and biodiesel from palm oil using homogeneous catalyst, i.e. an aqueous phase of ammonium molybdate, was studied. This catalyst was prepared by dissolving sodium molybdate in de-ionized water with hydrochloric acid, and then neutralizing the mixture with ammonium hydroxide. The solution was dried at 90 °C for 24 h to obtain ammonium molybdate. Then, characterization of the catalyst was done by informative techniques, such as XRD and FT-IR. The results showed that the main phase of the synthesized catalyst was molybdate ammonium hydrates (4MoO3.2NH3.H2O, and also bands of Mo–O, Mo–O–Mo, N–H and surface hydroxyl groups were observed in the sample. Moreover, activity test confirms that the bio-naphtha produced from the proposed method has a few aromatic components, and its sulfur content was negligible. Moreover, ash, nitrogen, sulfur and carbon residue were not detected in the produced biodiesel, and its Cetane index was 66.3. Therefore, it was a suitable fuel for diesel engines vehicles. Copyright © 2017 BCREC GROUP. All rights reserved Received: 3rd May 2016; Revised: 1st October 2016; Accepted: 18th October 2016 How to Cite: Sadighi, S., Targhi, S.K.M. (2017. Preparation of Biofuel from Palm Oil Catalyzed by Ammonium Molybdate in Homogeneous Phase. Bulletin of Chemical Reaction Engineering & Catalysis, 12 (1: 49-54 (doi:10.9767/bcrec.12.1.486.49-54 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.12.1.486.49-54

Nonlinear stochastic dynamics of mesoscopic homogeneous biochemical reaction systems—an analytical theory

International Nuclear Information System (INIS)

Qian, Hong

2011-01-01

The nonlinear dynamics of biochemical reactions in a small-sized system on the order of a cell are stochastic. Assuming spatial homogeneity, the populations of n molecular species follow a multi-dimensional birth-and-death process on Z n . We introduce the Delbrück–Gillespie process, a continuous-time Markov jump process, whose Kolmogorov forward equation has been known as the chemical master equation, and whose stochastic trajectories can be computed via the Gillespie algorithm. Using simple models, we illustrate that a system of nonlinear ordinary differential equations on R n emerges in the infinite system size limit. For finite system size, transitions among multiple attractors of the nonlinear dynamical system are rare events with exponentially long transit times. There is a separation of time scales between the deterministic ODEs and the stochastic Markov jumps between attractors. No diffusion process can provide a global representation that is accurate on both short and long time scales for the nonlinear, stochastic population dynamics. On the short time scale and near deterministic stable fixed points, Ornstein–Uhlenbeck Gaussian processes give linear stochastic dynamics that exhibit time-irreversible circular motion for open, driven chemical systems. Extending this individual stochastic behaviour-based nonlinear population theory of molecular species to other biological systems is discussed. (invited article)

Adsorption and catalysis: The effect of confinement on chemical reactions

International Nuclear Information System (INIS)

Santiso, Erik E.; George, Aaron M.; Turner, C. Heath; Kostov, Milen K.; Gubbins, Keith E.; Buongiorno-Nardelli, Marco; Sliwinska-Bartkowiak, MaIgorzata

2005-01-01

Confinement within porous materials can affect chemical reactions through a host of different effects, including changes in the thermodynamic state of the system due to interactions with the pore walls, selective adsorption, geometrical constraints that affect the reaction mechanism, electronic perturbation due to the substrate, etc. In this work, we present an overview of some of our recent research on some of these effects, on chemical equilibrium, kinetic rates and reaction mechanisms. We also discuss our current and future directions for research in this area

Time-resolved chromatographic analysis and mechanisms in adsorption and catalysis.

Science.gov (United States)

Roubani-Kalantzopoulou, Fani

2009-03-06

The main object of this review is the study of fundamentals of adsorption and heterogeneous catalysis, a benefit for the understanding of adsorptive and catalytic properties. This work aims to define and record, with the utmost accuracy, the phenomena and the possible reactions. A new methodology for the study of the adsorption is presented, which is a version of the well-known inverse gas chromatography. This reversed-flow inverse gas chromatography (RF-IGC) is technically very simple, and it is combined with a mathematical analysis that gives the possibility for the estimation of various physicochemical parameters related to adsorbent or catalyst characterization, under conditions compatible with the operation of real adsorbents and catalysts. On this base, this methodology has been successfully applied to the study of the impact of air pollutants, volatile organic and/or inorganic, on many solids such as marbles, ceramics, oxide-pigments of works of art, building materials, authentic statues of the Greek Archaeological Museums. Moreover, this methodology proved to be a powerful tool for studying the topography of active sites of heterogeneous surfaces in the nano-scale domain. Thus, some very important local quantities for the surface chemistry have been determined experimentally for many solids including thin films. These physicochemical local quantities (among which adsorption energy and entropy, surface diffusion coefficient, probability density function) have been determined from the experimental pairs of height of extra chromatographic peaks and time by a nonlinear least-squares method, through personal computer programs written in GW BASIC and lately in FORTRAN. Through the time-resolved analysis the surface characterization of the examined materials took place. In addition, the kinetic constants responsible for adsorption/desorption and surface chemical reactions have also been calculated. Thus, important answers have been provided to the following

Molecular surface science of heterogeneous catalysis. History and perspective

International Nuclear Information System (INIS)

Somorjai, G.A.

1983-08-01

A personal account is given of how the author became involved with modern surface science and how it was employed for studies of the chemistry of surfaces and heterogeneous catalysis. New techniques were developed for studying the properties of the surface monolayers: Auger electron spectroscopy, LEED, XPS, molecular beam surface scattering, etc. An apparatus was developed and used to study hydrocarbon conversion reactions on Pt, CO hydrogenation on Rh and Fe, and NH 3 synthesis on Fe. A model has been developed for the working Pt reforming catalyst. The three molecular ingredients that control catalytic properties are atomic surface structure, an active carbonaceous deposit, and the proper oxidation state of surface atoms. 40 references, 21 figures

Molecular surface science of heterogeneous catalysis. History and perspective

Energy Technology Data Exchange (ETDEWEB)

Somorjai, G.A.

1983-08-01

A personal account is given of how the author became involved with modern surface science and how it was employed for studies of the chemistry of surfaces and heterogeneous catalysis. New techniques were developed for studying the properties of the surface monolayers: Auger electron spectroscopy, LEED, XPS, molecular beam surface scattering, etc. An apparatus was developed and used to study hydrocarbon conversion reactions on Pt, CO hydrogenation on Rh and Fe, and NH/sub 3/ synthesis on Fe. A model has been developed for the working Pt reforming catalyst. The three molecular ingredients that control catalytic properties are atomic surface structure, an active carbonaceous deposit, and the proper oxidation state of surface atoms. 40 references, 21 figures. (DLC)

Preface: Catalysis Today

DEFF Research Database (Denmark)

Li, Yongdan

2016-01-01

This special issue of Catalysis Today with the theme “Sustain-able Energy” results from a great success of the session “Catalytic Technologies Accelerating the Establishment of Sustainable and Clean Energy”, one of the two sessions of the 1st International Symposium on Catalytic Science and Techn...

Nanotecnologia: aspectos gerais e potencial de aplicação em catálise Nanotechnology: general aspects and potential applications in catalysis

Directory of Open Access Journals (Sweden)

Hadma Sousa Ferreira

2009-01-01

Full Text Available In recent years nanomaterials, such as metallic nanoparticles, nanowires, nanotapes, nanotubes and nanocomposites, have attracted increasing interest for several technological applications. In catalysis, the great potential of nanomaterials is related to the high catalytic activity exhibited by these materials as a function of the high surface/volume ratio when the particles acquire diameter below 5 nm. In this work, a review about concepts and background of nanoscience and nanotechnology is presented with emphasis in catalysis. Special attention is given to gold nanoparticles and carbon nanotubes, focusing the properties and characteristics of these materials in several catalytic reactions.

Electric-field enhanced performance in catalysis and solid-state devices involving gases

Science.gov (United States)

Blackburn, Bryan M.; Wachsman, Eric D.; Van Assche, IV, Frederick Martin

2015-05-19

Electrode configurations for electric-field enhanced performance in catalysis and solid-state devices involving gases are provided. According to an embodiment, electric-field electrodes can be incorporated in devices such as gas sensors and fuel cells to shape an electric field provided with respect to sensing electrodes for the gas sensors and surfaces of the fuel cells. The shaped electric fields can alter surface dynamics, system thermodynamics, reaction kinetics, and adsorption/desorption processes. In one embodiment, ring-shaped electric-field electrodes can be provided around sensing electrodes of a planar gas sensor.

Positron studies in catalysis research

International Nuclear Information System (INIS)

1994-01-01

During the past eight months, the authors have made progress in several areas relevant to the eventual use of positron techniques in catalysis research. They have come closer to the completion of their positron microscope, and at the same time have performed several studies in their non-microscopic positron spectrometer which should ultimately be applicable to catalysis. The current status of the efforts in each of these areas is summarized in the following sections: Construction of the positron microscope (optical element construction, data collection software, and electronic sub-assemblies); Doppler broadening spectroscopy of metal silicide; Positron lifetime spectroscopy of glassy polymers; and Positron lifetime measurements of pore-sizes in zeolites

Vision 2020. Reaction Engineering Roadmap

Energy Technology Data Exchange (ETDEWEB)

Klipstein, David H. [Reaction Design, San Diego, CA (United States); Robinson, Sharon [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

2001-01-01

The Reaction Engineering Roadmap is a part of an industry- wide effort to create a blueprint of the research and technology milestones that are necessary to achieve longterm industry goals. This report documents the results of a workshop focused on the research needs, technology barriers, and priorities of the chemical industry as they relate to reaction engineering viewed first by industrial use (basic chemicals; specialty chemicals; pharmaceuticals; and polymers) and then by technology segment (reactor system selection, design, and scale-up; chemical mechanism development and property estimation; dealing with catalysis; and new, nonstandard reactor types).

Cyclopropanation of 5-(1-Bromo-2-phenyl-vinyl-3-methyl-4-nitro-isoxazoles under Phase Transfer Catalysis (PTC Conditions

Directory of Open Access Journals (Sweden)

Linda Piras

2015-04-01

Full Text Available Heavily substituted cyclopropane esters were prepared in high yields, complete diastereoselection and average (up to 58% enantioselectivity. The reaction described herein entailed reacting 4-nitro-5-bromostyrylisoxazoles, a class of powerful Michael acceptors with malonate esters under the catalysis of 5 mol% of a chincona derived phase-transfer catalyst.

Benchmarking the Stability of Oxygen Evolution Reaction Catalysts

DEFF Research Database (Denmark)

Frydendal, Rasmus; Paoli, Elisa Antares; Knudsen, Brian Peter

2014-01-01

Because of the rising need for energy storage, potentially facilitated by electrolyzers, improvements to the catalysis of the oxygen evolution reaction (OER) become increasingly relevant. Standardized protocols have been developed for determining critical figures of merit, such as the electrochem......Because of the rising need for energy storage, potentially facilitated by electrolyzers, improvements to the catalysis of the oxygen evolution reaction (OER) become increasingly relevant. Standardized protocols have been developed for determining critical figures of merit...... coupled plasma mass spectrometry (ICP–MS). We show that a meaningful estimation of the stability cannot be achieved based on purely electrochemical tests. On the catalysts tested, the anodic dissolution current was four orders of magnitude lower than the total current. We propose that even if long......-term testing cannot be replaced, a useful evaluation of the stability can be achieved with short-term tests by using EQCM or ICP–MS....

Spatially resolved observation of crystal-face-dependent catalysis by single turnover counting

Science.gov (United States)

Roeffaers, Maarten B. J.; Sels, Bert F.; Uji-I, Hiroshi; de Schryver, Frans C.; Jacobs, Pierre A.; de Vos, Dirk E.; Hofkens, Johan

2006-02-01

Catalytic processes on surfaces have long been studied by probing model reactions on single-crystal metal surfaces under high vacuum conditions. Yet the vast majority of industrial heterogeneous catalysis occurs at ambient or elevated pressures using complex materials with crystal faces, edges and defects differing in their catalytic activity. Clearly, if new or improved catalysts are to be rationally designed, we require quantitative correlations between surface features and catalytic activity-ideally obtained under realistic reaction conditions. Transmission electron microscopy and scanning tunnelling microscopy have allowed in situ characterization of catalyst surfaces with atomic resolution, but are limited by the need for low-pressure conditions and conductive surfaces, respectively. Sum frequency generation spectroscopy can identify vibrations of adsorbed reactants and products in both gaseous and condensed phases, but so far lacks sensitivity down to the single molecule level. Here we adapt real-time monitoring of the chemical transformation of individual organic molecules by fluorescence microscopy to monitor reactions catalysed by crystals of a layered double hydroxide immersed in reagent solution. By using a wide field microscope, we are able to map the spatial distribution of catalytic activity over the entire crystal by counting single turnover events. We find that ester hydrolysis proceeds on the lateral {1010} crystal faces, while transesterification occurs on the entire outer crystal surface. Because the method operates at ambient temperature and pressure and in a condensed phase, it can be applied to the growing number of liquid-phase industrial organic transformations to localize catalytic activity on and in inorganic solids. An exciting opportunity is the use of probe molecules with different size and functionality, which should provide insight into shape-selective or structure-sensitive catalysis and thus help with the rational design of new or

Sustainable green catalysis by supported metal nanoparticles.

Science.gov (United States)

Fukuoka, Atsushi; Dhepe, Paresh L

2009-01-01

The recent progress of sustainable green catalysis by supported metal nanoparticles is described. The template synthesis of metal nanoparticles in ordered porous materials is studied for the rational design of heterogeneous catalysts capable of high activity and selectivity. The application of these materials in green catalytic processes results in a unique activity and selectivity arising from the concerted effect of metal nanoparticles and supports. The high catalytic performances of Pt nanoparticles in mesoporous silica is reported. Supported metal catalysts have also been applied to biomass conversion by heterogeneous catalysis. Additionally, the degradation of cellulose by supported metal catalysts, in which bifunctional catalysis of acid and metal plays the key role for the hydrolysis and reduction of cellulose, is also reported. Copyright 2009 The Japan Chemical Journal Forum and Wiley Periodicals, Inc.

Diffusion piecewise homogenization via flux discontinuity ratios

International Nuclear Information System (INIS)

Sanchez, Richard; Dante, Giorgio; Zmijarevic, Igor

2013-01-01

We analyze piecewise homogenization with flux-weighted cross sections and preservation of averaged currents at the boundary of the homogenized domain. Introduction of a set of flux discontinuity ratios (FDR) that preserve reference interface currents leads to preservation of averaged region reaction rates and fluxes. We consider the class of numerical discretizations with one degree of freedom per volume and per surface and prove that when the homogenization and computing meshes are equal there is a unique solution for the FDRs which exactly preserve interface currents. For diffusion sub-meshing we introduce a Jacobian-Free Newton-Krylov method and for all cases considered obtain an 'exact' numerical solution (eight digits for the interface currents). The homogenization is completed by extending the familiar full assembly homogenization via flux discontinuity factors to the sides of regions laying on the boundary of the piecewise homogenized domain. Finally, for the familiar nodal discretization we numerically find that the FDRs obtained with no sub-mesh (nearly at no cost) can be effectively used for whole-core diffusion calculations with sub-mesh. This is not the case, however, for cell-centered finite differences. (authors)

Bridging the Gap: From Model Surfaces to Nanoparticle Analogs for Selective Oxidation and Steam Reforming of Methanol and Selective Hydrogenation Catalysis

Science.gov (United States)

Boucher, Matthew B.

Most industrial catalysts are very complex, comprising of non-uniform materials with varying structures, impurities, and interaction between the active metal and supporting substrate. A large portion of the ongoing research in heterogeneous catalysis focuses on understanding structure-function relationships in catalytic materials. In parallel, there is a large area of surface science research focused on studying model catalytic systems for which structural parameters can be tuned and measured with high precision. It is commonly argued, however, that these systems are oversimplified, and that observations made in model systems do not translate to robust catalysts operating in practical environments; this discontinuity is often referred to as a "gap." The focus of this thesis is to explore the mutual benefits of surface science and catalysis, or "bridge the gap," by studying two catalytic systems in both ultra-high vacuum (UHV) and near ambient-environments. The first reaction is the catalytic steam reforming of methanol (SRM) to hydrogen and carbon dioxide. The SRM reaction is a promising route for on-demand hydrogen production. For this catalytic system, the central hypothesis in this thesis is that a balance between redox capability and weak binding of reaction intermediates is necessary for high SRM activity and selectivity to carbon dioxide. As such, a new catalyst for the SRM reaction is developed which incorporates very small amounts of gold (liquid-phase, stirred-tank batch reactor under a hydrogen head pressure of approximately 7 bar. Palladium alloyed into the surface of otherwise inactive copper nanoparticles shows a marked improvement in selectivity when compared to monometallic palladium catalysts with the same metal loading. This effect is attributed hydrogen spillover onto the copper surface. In summary, the development of new, highly active and selective catalysts for the methanol steam reforming reaction and for the partial hydrogenation of alkynes

Detection of Reaction Intermediates in Mg2+-Dependent DNA Synthesis and RNA Degradation by Time-Resolved X-Ray Crystallography.

Science.gov (United States)

Samara, Nadine L; Gao, Yang; Wu, Jinjun; Yang, Wei

2017-01-01

Structures of enzyme-substrate/product complexes have been studied for over four decades but have been limited to either before or after a chemical reaction. Recently using in crystallo catalysis combined with X-ray diffraction, we have discovered that many enzymatic reactions in nucleic acid metabolism require additional metal ion cofactors that are not present in the substrate or product state. By controlling metal ions essential for catalysis, the in crystallo approach has revealed unprecedented details of reaction intermediates. Here we present protocols used for successful studies of Mg 2+ -dependent DNA polymerases and ribonucleases that are applicable to analyses of a variety of metal ion-dependent reactions. © 2017 Elsevier Inc. All rights reserved.

Recent Developments of Electrochemical Promotion of Catalysis in the Techniques of DeNOx

Directory of Open Access Journals (Sweden)

Xiaolong Tang

2013-01-01

Full Text Available Electrochemical promotion of catalysis reactions (EPOC is one of the most significant discoveries in the field of catalytic and environmental protection. The work presented in this paper focuses on the aspects of reaction mechanism, influencing factors, and recent positive results. It has been shown with more than 80 different catalytic systems that the catalytic activity and selectivity of conductive catalysts deposited on solid electrolytes can be altered in the last 30 years. The active ingredient of catalyst can be activated by applying constant voltage or constant current to the catalysts/electrolyte interface. The effect of EPOC can improve greatly the conversion rate of NOx. And it can also improve the lifetime of catalyst by inhibiting its poisoning.

Accumulative charge separation for solar fuels production: coupling light-induced single electron transfer to multielectron catalysis.

Science.gov (United States)

Hammarström, Leif

2015-03-17

The conversion and storage of solar energy into a fuel holds promise to provide a significant part of the future renewable energy demand of our societies. Solar energy technologies today generate heat or electricity, while the large majority of our energy is used in the form of fuels. Direct conversion of solar energy to a fuel would satisfy our needs for storable energy on a large scale. Solar fuels can be generated by absorbing light and converting its energy to chemical energy by electron transfer leading to separation of electrons and holes. The electrons are used in the catalytic reduction of a cheap substrate with low energy content into a high-energy fuel. The holes are filled by oxidation of water, which is the only electron source available for large scale solar fuel production. Absorption of a single photon typically leads to separation of a single electron-hole pair. In contrast, fuel production and water oxidation are multielectron, multiproton reactions. Therefore, a system for direct solar fuel production must be able to accumulate the electrons and holes provided by the sequential absorption of several photons in order to complete the catalytic reactions. In this Account, the process is termed accumulative charge separation. This is considerably more complicated than charge separation on a single electron level and needs particular attention. Semiconductor materials and molecular dyes have for a long time been optimized for use in photovoltaic devices. Efforts are made to develop new systems for light harvesting and charge separation that are better optimized for solar fuel production than those used in the early devices presented so far. Significant progress has recently been made in the discovery and design of better homogeneous and heterogeneous catalysts for solar fuels and water oxidation. While the heterogeneous ones perform better today, molecular catalysts based on transition metal complexes offer much greater tunability of electronic and

Synthesis of silica nanosphere from homogeneous and ...

Indian Academy of Sciences (India)

WINTEC

avoid it, reaction in heterogeneous system using CTABr was carried out. Nanosized silica sphere with ... Homogeneous system contains a mixture of ethanol, water, aqueous ammonia and ... heated to 823 K (rate, 1 K/min) in air and kept at this.

Niobium bonds as homogeneous catalysts for the cyclotrimerization of alkynes

International Nuclear Information System (INIS)

Du Toit, C.J.

1984-05-01

The activity and selectivity of the catalytic system MX 5 with M = Nb or Ta and X = Cl - or Br - and (CH 3 ) 3 TaCl 2 with regard to the reaction rate and product formation in the reaction with alkynes were evaluated. A measuring technique was developed with which the reaction path of the oligomerization reactions of alkynes with homogeneous catalysts in a nitrogen atmosphere can be followed spectrophotometrically

A molecular view of heterogeneous catalysis

DEFF Research Database (Denmark)

Christensen, Claus H.; Nørskov, Jens Kehlet

2008-01-01

The establishment of a molecular view of heterogeneous catalysis has been hampered for a number of reasons. There are, however, recent developments, which show that we are now on the way towards reaching a molecular-scale picture of the way solids work as catalysts. By a combination of new...... by enabling a rational design of new catalysts. We illustrate this important development in heterogeneous catalysis by highlighting recent examples of catalyst systems for which it has been possible to achieve such a detailed understanding. In particular, we emphasize examples where this progress has made...

Density functional theory studies of transition metal nanoparticles in catalysis

DEFF Research Database (Denmark)

Greeley, Jeffrey Philip; Rankin, Rees; Zeng, Zhenhua

2013-01-01

Periodic Density Functional Theory calculations are capable of providing powerful insights into the structural, energetics, and electronic phenomena that underlie heterogeneous catalysis on transition metal nanoparticles. Such calculations are now routinely applied to single crystal metal surfaces...... and to subnanometer metal clusters. Descriptions of catalysis on truly nanosized structures, however, are generally not as well developed. In this talk, I will illustrate different approaches to analyzing nanocatalytic phenomena with DFT calculations. I will describe case studies from heterogeneous catalysis...... and electrocatalysis, in which single crystal models are combined with Wulff construction-based ideas to produce descriptions of average nanocatalyst behavior. Then, I will proceed to describe explicitly DFT-based descriptions of catalysis on truly nanosized particles (

Atomically precise cluster catalysis towards quantum controlled catalysts

International Nuclear Information System (INIS)

Watanabe, Yoshihide

2014-01-01

Catalysis of atomically precise clusters supported on a substrate is reviewed in relation to the type of reactions. The catalytic activity of supported clusters has generally been discussed in terms of electronic structure. Several lines of evidence have indicated that the electronic structure of clusters and the geometry of clusters on a support, including the accompanying cluster-support interaction, are strongly correlated with catalytic activity. The electronic states of small clusters would be easily affected by cluster–support interactions. Several studies have suggested that it is possible to tune the electronic structure through atomic control of the cluster size. It is promising to tune not only the number of cluster atoms, but also the hybridization between the electronic states of the adsorbed reactant molecules and clusters in order to realize a quantum-controlled catalyst. (review)

Lewis acid catalysis of a Diels-Alder reaction in water

NARCIS (Netherlands)

Otto, S; Bertoncin, F; Engberts, JBFN

1996-01-01

Here we report the first detailed study of a Diels-Alder (DA) reaction that is catalyzed by Lewis acids in water. The effect of Co2+, Ni2+, Cu2+ and Zn2+ ions as Lewis acid catalysts on the rate and endo-exo selectivity of the DA reaction between the bidentate dienophiles

Prebiotic RNA Synthesis by Montmorillonite Catalysis

Directory of Open Access Journals (Sweden)

Sohan Jheeta

2014-08-01

Full Text Available This review summarizes our recent findings on the role of mineral salts in prebiotic RNA synthesis, which is catalyzed by montmorillonite clay minerals. The clay minerals not only catalyze the synthesis of RNA but also facilitate homochiral selection. Preliminary data of these findings have been presented at the “Horizontal Gene Transfer and the Last Universal Common Ancestor (LUCA” conference at the Open University, Milton Keynes, UK, 5–6 September 2013. The objective of this meeting was to recognize the significance of RNA in LUCA. We believe that the prebiotic RNA synthesis from its monomers must have been a simple process. As a first step, it may have required activation of the 5'-end of the mononucleotide with a leaving group, e.g., imidazole in our model reaction (Figure 1. Wide ranges of activating groups are produced from HCN under plausible prebiotic Earth conditions. The final step is clay mineral catalysis in the presence of mineral salts to facilitate selective production of functional RNA. Both the clay minerals and mineral salts would have been abundant on early Earth. We have demonstrated that while montmorillonite (pH 7 produced only dimers from its monomers in water, addition of sodium chloride (1 M enhanced the chain length multifold, as detected by HPLC. The effect of monovalent cations on RNA synthesis was of the following order: Li+ > Na+ > K+. A similar effect was observed with the anions, enhancing catalysis in the following order: Cl− > Br− > I−. The montmorillonite-catalyzed RNA synthesis was not affected by hydrophobic or hydrophilic interactions. We thus show that prebiotic synthesis of RNA from its monomers was a simple process requiring only clay minerals and a small amount of salt.

On the mechanism of hydrogen evolution catalysis by proteins: A case study with bovine serum albumin

Czech Academy of Sciences Publication Activity Database

Doneux, T.; Ostatná, Veronika; Paleček, Emil

2011-01-01

Roč. 56, č. 25 (2011), s. 9337-9343 ISSN 0013-4686 R&D Projects: GA MŠk(CZ) ME09038; GA MŠk(CZ) LC06035 Grant - others:GA ČR(CZ) GAP301/11/2055 Institutional research plan: CEZ:AV0Z50040507; CEZ:AV0Z50040702 Keywords : hydrogen evolution reaction * mediated catalysis * proton transfer Subject RIV: BO - Biophysics Impact factor: 3.832, year: 2011

A computational analysis on homogeneous-heterogeneous mechanism in Carreau fluid flow

Science.gov (United States)

Khan, Imad; Rehman, Khalil Ur; Malik, M. Y.; Shafquatullah

2018-03-01

In this article magnetohydrodynamic Carreau fluid flow towards stretching cylinder is considered in the presence of homogeneous-heterogeneous reactions effect. The flow model is structured by utilizing theoretical grounds. For the numerical solution a shooting method along with Runge-Kutta algorithm is executed. The outcomes are provided through graphs. It is observed that the Carreau fluid concentration shows decline values via positive iterations of homogeneous-heterogeneous reaction parameters towards both shear thinning and thickening case. The present work is certified through comparison with already existing literature in a limiting sense.

REALCAT: A New Platform to Bring Catalysis to the Lightspeed

Directory of Open Access Journals (Sweden)

Paul Sébastien

2015-03-01

Full Text Available Catalysis, irrespective of its form can be considered as one of the most important pillars of today’s chemical industry. The development of new catalysts with improved performances is therefore a highly strategic issue. However, the a priori theoretical design of the best catalyst for a desired reaction is not yet possible and a time- and money-consuming experimental phase is still needed to develop a new catalyst for a given reaction. The REALCAT platform described in this paper consists in a complete, unique, integrated and top-level high-throughput technologies workflow that allows a significant acceleration of this kind of research. This is illustrated by some preliminary results of optimization of the operating conditions of glycerol dehydration to acrolein over an heteropolyacid-based supported catalyst. It is shown that using REALCAT high-throughput tools a more than 10-fold acceleration of the operating conditions optimization process is obtained.

Rh(II)-catalyzed reactions of differentially substituted bis(diazo) functionalities.

Science.gov (United States)

Bonderoff, Sara A; Padwa, Albert

2013-08-16

The chemoselective reaction of donor/acceptor (D/A) and acceptor/acceptor (A/A) diazo moieties in the same molecule was examined using 3-diazo-1-(ethyl 2-diazomalonyl)indolin-2-one under rhodium(II) catalysis. The D/A diazo group undergoes selective cyclopropanation as well as XH-insertion, leaving behind the second diazo group for a further intramolecular dipolar cycloaddition reaction.

Cooperative catalysis with block copolymer micelles: A combinatorial approach

KAUST Repository

Bukhryakov, Konstantin V.

2015-02-09

A rapid approach to identifying complementary catalytic groups using combinations of functional polymers is presented. Amphiphilic polymers with "clickable" hydrophobic blocks were used to create a library of functional polymers, each bearing a single functionality. The polymers were combined in water, yielding mixed micelles. As the functional groups were colocalized in the hydrophobic microphase, they could act cooperatively, giving rise to new modes of catalysis. The multipolymer "clumps" were screened for catalytic activity, both in the presence and absence of metal ions. A number of catalyst candidates were identified across a wide range of model reaction types. One of the catalytic systems discovered was used to perform a number of preparative-scale syntheses. Our approach provides easy access to a range of enzyme-inspired cooperative catalysts.

Cooperative catalysis with block copolymer micelles: A combinatorial approach

KAUST Repository

Bukhryakov, Konstantin V.; Desyatkin, Victor G.; O'Shea, John Paul; Almahdali, Sarah; Solovyeva, Vera; Rodionov, Valentin

2015-01-01

A rapid approach to identifying complementary catalytic groups using combinations of functional polymers is presented. Amphiphilic polymers with "clickable" hydrophobic blocks were used to create a library of functional polymers, each bearing a single functionality. The polymers were combined in water, yielding mixed micelles. As the functional groups were colocalized in the hydrophobic microphase, they could act cooperatively, giving rise to new modes of catalysis. The multipolymer "clumps" were screened for catalytic activity, both in the presence and absence of metal ions. A number of catalyst candidates were identified across a wide range of model reaction types. One of the catalytic systems discovered was used to perform a number of preparative-scale syntheses. Our approach provides easy access to a range of enzyme-inspired cooperative catalysts.

Catalysis in high-temperature fuel cells.

Science.gov (United States)

Föger, K; Ahmed, K

2005-02-17

Catalysis plays a critical role in solid oxide fuel cell systems. The electrochemical reactions within the cell--oxygen dissociation on the cathode and electrochemical fuel combustion on the anode--are catalytic reactions. The fuels used in high-temperature fuel cells, for example, natural gas, propane, or liquid hydrocarbons, need to be preprocessed to a form suitable for conversion on the anode-sulfur removal and pre-reforming. The unconverted fuel (economic fuel utilization around 85%) is commonly combusted using a catalytic burner. Ceramic Fuel Cells Ltd. has developed anodes that in addition to having electrochemical activity also are reactive for internal steam reforming of methane. This can simplify fuel preprocessing, but its main advantage is thermal management of the fuel cell stack by endothermic heat removal. Using this approach, the objective of fuel preprocessing is to produce a methane-rich fuel stream but with all higher hydrocarbons removed. Sulfur removal can be achieved by absorption or hydro-desulfurization (HDS). Depending on the system configuration, hydrogen is also required for start-up and shutdown. Reactor operating parameters are strongly tied to fuel cell operational regimes, thus often limiting optimization of the catalytic reactors. In this paper we discuss operation of an authothermal reforming reactor for hydrogen generation for HDS and start-up/shutdown, and development of a pre-reformer for converting propane to a methane-rich fuel stream.

Beyond the volcano limitations in electrocatalysis - oxygen evolution reaction

DEFF Research Database (Denmark)

Halck, Niels Bendtsen; Petrykin, Valery; Krtil, Petr

2014-01-01

Oxygen evolution catalysis is restricted by the interdependence of adsorption energies of the reaction intermediates and the surface reactivity. The interdependence reduces the number of degrees of freedom available for catalyst optimization. Here it is demonstrated that this limitation can be re...

Out-of-equilibrium catalysis of chemical reactions by electronic tunnel currents.

Science.gov (United States)

Dzhioev, Alan A; Kosov, Daniel S; von Oppen, Felix

2013-04-07

We present an escape rate theory for current-induced chemical reactions. We use Keldysh nonequilibrium Green's functions to derive a Langevin equation for the reaction coordinate. Due to the out of equilibrium electronic degrees of freedom, the friction, noise, and effective temperature in the Langevin equation depend locally on the reaction coordinate. As an example, we consider the dissociation of diatomic molecules induced by the electronic current from a scanning tunnelling microscope tip. In the resonant tunnelling regime, the molecular dissociation involves two processes which are intricately interconnected: a modification of the potential energy barrier and heating of the molecule. The decrease of the molecular barrier (i.e., the current induced catalytic reduction of the barrier) accompanied by the appearance of the effective, reaction-coordinate-dependent temperature is an alternative mechanism for current-induced chemical reactions, which is distinctly different from the usual paradigm of pumping vibrational degrees of freedom.

High Throughput Sample Preparation and Analysis for DNA Sequencing, PCR and Combinatorial Screening of Catalysis Based on Capillary Array Technique

Energy Technology Data Exchange (ETDEWEB)

Zhang, Yonghua [Iowa State Univ., Ames, IA (United States)

2000-01-01

Sample preparation has been one of the major bottlenecks for many high throughput analyses. The purpose of this research was to develop new sample preparation and integration approach for DNA sequencing, PCR based DNA analysis and combinatorial screening of homogeneous catalysis based on multiplexed capillary electrophoresis with laser induced fluorescence or imaging UV absorption detection. The author first introduced a method to integrate the front-end tasks to DNA capillary-array sequencers. protocols for directly sequencing the plasmids from a single bacterial colony in fused-silica capillaries were developed. After the colony was picked, lysis was accomplished in situ in the plastic sample tube using either a thermocycler or heating block. Upon heating, the plasmids were released while chromsomal DNA and membrane proteins were denatured and precipitated to the bottom of the tube. After adding enzyme and Sanger reagents, the resulting solution was aspirated into the reaction capillaries by a syringe pump, and cycle sequencing was initiated. No deleterious effect upon the reaction efficiency, the on-line purification system, or the capillary electrophoresis separation was observed, even though the crude lysate was used as the template. Multiplexed on-line DNA sequencing data from 8 parallel channels allowed base calling up to 620 bp with an accuracy of 98%. The entire system can be automatically regenerated for repeated operation. For PCR based DNA analysis, they demonstrated that capillary electrophoresis with UV detection can be used for DNA analysis starting from clinical sample without purification. After PCR reaction using cheek cell, blood or HIV-1 gag DNA, the reaction mixtures was injected into the capillary either on-line or off-line by base stacking. The protocol was also applied to capillary array electrophoresis. The use of cheaper detection, and the elimination of purification of DNA sample before or after PCR reaction, will make this approach an

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

Energy Technology Data Exchange (ETDEWEB)

Hong, Yongchun; Wang, Yong

2017-09-01

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

Boosting Chemical Stability, Catalytic Activity, and Enantioselectivity of Metal-Organic Frameworks for Batch and Flow Reactions.

Science.gov (United States)

Chen, Xu; Jiang, Hong; Hou, Bang; Gong, Wei; Liu, Yan; Cui, Yong

2017-09-27

A key challenge in heterogeneous catalysis is the design and synthesis of heterogeneous catalysts featuring high catalytic activity, selectivity, and recyclability. Here we demonstrate that high-performance heterogeneous asymmetric catalysts can be engineered from a metal-organic framework (MOF) platform by using a ligand design strategy. Three porous chiral MOFs with the framework formula [Mn 2 L(H 2 O) 2 ] are prepared from enantiopure phosphono-carboxylate ligands of 1,1'-biphenol that are functionalized with 3,5-bis(trifluoromethyl)-, bismethyl-, and bisfluoro-phenyl substituents at the 3,3'-position. For the first time, we show that not only chemical stability but also catalytic activity and stereoselectivity of the MOFs can be tuned by modifying the ligand structures. Particularly, the MOF incorporated with -CF 3 groups on the pore walls exhibits enhanced tolerance to water, weak acid, and base compared with the MOFs with -F and -Me groups. Under both batch and flow reaction systems, the CF 3 -containing MOF demonstrated excellent reactivity, selectivity, and recyclability, affording high yields and enantioselectivities for alkylations of indoles and pyrrole with a range of ketoesters or nitroalkenes. In contrast, the corresponding homogeneous catalysts gave low enantioselectivity in catalyzing the tested reactions.

Staphylococcus aureus DNA ligase: characterization of its kinetics of catalysis and development of a high-throughput screening compatible chemiluminescent hybridization protection assay.

Science.gov (United States)

Gul, Sheraz; Brown, Richard; May, Earl; Mazzulla, Marie; Smyth, Martin G; Berry, Colin; Morby, Andrew; Powell, David J

2004-11-01

DNA ligases are key enzymes involved in the repair and replication of DNA. Prokaryotic DNA ligases uniquely use NAD+ as the adenylate donor during catalysis, whereas eukaryotic enzymes use ATP. This difference in substrate specificity makes the bacterial enzymes potential targets for therapeutic intervention. We have developed a homogeneous chemiluminescence-based hybridization protection assay for Staphylococcus aureus DNA ligase that uses novel acridinium ester technology and demonstrate that it is an alternative to the commonly used radiometric assays for ligases. The assay has been used to determine a number of kinetic constants for S. aureus DNA ligase catalysis. These included the K(m) values for NAD+ (2.75+/-0.1 microM) and the acridinium-ester-labelled DNA substrate (2.5+/-0.2 nM). A study of the pH-dependencies of kcat, K(m) and kcat/K(m) has revealed values of kinetically influential ionizations within the enzyme-substrate complexes (kcat) and free enzyme (kcat/K(m)). In each case, the curves were shown to be composed of one kinetically influential ionization, for k(cat), pK(a)=6.6+/-0.1 and kcat/K(m), pK(a)=7.1+/-0.1. Inhibition characteristics of the enzyme against two Escherichia coli DNA ligase inhibitors have also been determined with IC50 values for these being 3.30+/-0.86 microM for doxorubicin and 1.40+/-0.07 microM for chloroquine diphosphate. The assay has also been successfully miniaturized to a sufficiently low volume to allow it to be utilized in a high-throughput screen (384-well format; 20 microl reaction volume), enabling the assay to be used in screening campaigns against libraries of compounds to discover leads for further drug development.

Efficient Construction of Energetic Materials via Nonmetallic Catalytic Carbon-Carbon Cleavage/Oxime-Release-Coupling Reactions.

Science.gov (United States)

Zhao, Gang; He, Chunlin; Yin, Ping; Imler, Gregory H; Parrish, Damon A; Shreeve, Jean'ne M

2018-03-14

The exploitation of C-C activation to facilitate chemical reactions is well-known in organic chemistry. Traditional strategies in homogeneous media rely upon catalyst-activated or metal-mediated C-C bonds leading to the design of new processes for applications in organic chemistry. However, activation of a C-C bond, compared with C-H bond activation, is a more challenging process and an underdeveloped area because thermodynamics does not favor insertion into a C-C bond in solution. Carbon-carbon bond cleavage through loss of an oxime moiety has not been reported. In this paper, a new observation of self-coupling via C-C bond cleavage with concomitant loss of oxime in the absence of metals (either metal-complex mediation or catalysis) results in dihydroxylammonium 5,5-bistetrazole-1,10-diolate (TKX-50) as well as N, N'-([3,3'-bi(1,2,4-oxadiazole)]-5,5'-diyl)dinitramine, a potential candidate for a new generation of energetic materials.

Multiple Hydrogen-Bond Activation in Asymmetric Brønsted Acid Catalysis

KAUST Repository

Liao, Hsuan-Hung

2018-05-03

An efficient protocol for the asymmetric synthesis of chiral tetrahydroquinolines bearing multiple stereogenic centers by means of asymmetric Brønsted acid catalysis was developed. A chiral 1,1′‐spirobiindane‐7,7′‐diol (SPINOL)‐based N‐triflylphosphoramide (NTPA) proved to be an effective Brønsted acid catalyst for the in situ generation of aza‐ortho‐quinone methides (aza‐o‐QMs) and their subsequent cycloaddition reaction with unactivated alkenes to provide the products with excellent diastereo‐ and enantioselectivities. In addition, DFT calculations provided insight into the activation mode and nature of the interactions between the N‐triflylphosphoramide catalyst and the generated aza‐o‐QMs.

Multiple Hydrogen-Bond Activation in Asymmetric Brønsted Acid Catalysis

KAUST Repository

Liao, Hsuan-Hung; Hsiao, Chien-Chi; Atodiresei, Iuliana; Rueping, Magnus

2018-01-01

An efficient protocol for the asymmetric synthesis of chiral tetrahydroquinolines bearing multiple stereogenic centers by means of asymmetric Brønsted acid catalysis was developed. A chiral 1,1′‐spirobiindane‐7,7′‐diol (SPINOL)‐based N‐triflylphosphoramide (NTPA) proved to be an effective Brønsted acid catalyst for the in situ generation of aza‐ortho‐quinone methides (aza‐o‐QMs) and their subsequent cycloaddition reaction with unactivated alkenes to provide the products with excellent diastereo‐ and enantioselectivities. In addition, DFT calculations provided insight into the activation mode and nature of the interactions between the N‐triflylphosphoramide catalyst and the generated aza‐o‐QMs.

DNA-based catalytic enantioselective intermolecular oxa-Michael addition reactions

NARCIS (Netherlands)

Megens, Rik P.; Roelfes, Gerard

2012-01-01

Using the DNA-based catalysis concept, a novel Cu(II) catalyzed enantioselective oxa-Michael addition of alcohols to enones is reported. Enantioselectivities of up to 86% were obtained. The presence of water is important for the reactivity, possibly by reverting unwanted side reactions such as

Bulk gold catalyzed oxidation reactions of amines and isocyanides and iron porphyrin catalyzed N-H and O-H bond insertion/cyclization reactions of diamines and aminoalcohols

Energy Technology Data Exchange (ETDEWEB)

Klobukowski, Erik [Iowa State Univ., Ames, IA (United States)

2011-01-01

This work involves two projects. The first project entails the study of bulk gold as a catalyst in oxidation reactions of isocyanides and amines. The main goal of this project was to study the activation and reactions of molecules at metal surfaces in order to assess how organometallic principles for homogeneous processes apply to heterogeneous catalysis. Since previous work had used oxygen as an oxidant in bulk gold catalyzed reactions, the generality of gold catalysis with other oxidants was examined. Amine N-oxides were chosen for study, due to their properties and use in the oxidation of carbonyl ligands in organometallic complexes. When amine N-oxides were used as an oxidant in the reaction of isocyanides with amines, the system was able to produce ureas from a variety of isocyanides, amines, and amine N-oxides. In addition, the rate was found to generally increase as the amine N-oxide concentration increased, and decrease with increased concentrations of the amine. Mechanistic studies revealed that the reaction likely involves transfer of an oxygen atom from the amine N-oxide to the adsorbed isocyanide to generate an isocyanate intermediate. Subsequent nucleophilic attack by the amine yields the urea. This is in contrast to the bulk gold-catalyzed reaction mechanism of isocyanides with amines and oxygen. Formation of urea in this case was proposed to proceed through a diaminocarbene intermediate. Moreover, formation of the proposed isocyanate intermediate is consistent with the reactions of metal carbonyl ligands, which are isoelectronic to isocyanides. Nucleophilic attack at coordinated CO by amine N-oxides produces CO{sub 2} and is analogous to the production of an isocyanate in this gold system. When the bulk gold-catalyzed oxidative dehydrogenation of amines was examined with amine N-oxides, the same products were afforded as when O{sub 2} was used as the oxidant. When the two types of oxidants were directly compared using the same reaction system and

Modeling the reactions catalyzed by coenzyme B12-dependent enzymes.

Science.gov (United States)

Sandala, Gregory M; Smith, David M; Radom, Leo

2010-05-18

Enzymes accelerate chemical reactions with an exceptional selectivity that makes life itself possible. Understanding the factors responsible for this efficient catalysis is of utmost importance in our quest to harness the tremendous power of enzymes. Computational chemistry has emerged as an important adjunct to experimental chemistry and biochemistry in this regard, because it provides detailed insights into the relationship between structure and function in a systematic and straightforward manner. In this Account, we highlight our recent high-level theoretical investigations toward this end in studying the radical-based reactions catalyzed by enzymes dependent on coenzyme B(12) (or adenosylcobalamin, AdoCbl). In addition to their fundamental position in biology, the AdoCbl-dependent enzymes represent a valuable framework within which to understand Nature's method of efficiently handling high-energy species to execute very specific reactions. The AdoCbl-mediated reactions are characterized by the interchange of a hydrogen atom and a functional group on adjacent carbon atoms. Our calculations are consistent with the conclusion that the main role of AdoCbl is to provide a source of radicals, thus moving the 1,2-rearrangements onto the radical potential energy surface. Our studies also show that the radical rearrangement step is facilitated by partial proton transfer involving the substrate. Specifically, we observe that the energy requirements for radical rearrangement are reduced dramatically with appropriate partial protonation or partial deprotonation or sometimes (synergistically) both. Such interactions are particularly relevant to enzyme catalysis, because it is likely that the local amino acid environment in the active site of an enzyme can function in this capacity through hydrogen bonding. Finally, our calculations indicate that the intervention of a very stable radical along the reaction pathway may inactivate the enzyme, demonstrating that sustained

A multifunctional microwave plasma reaction apparatus and its applications

International Nuclear Information System (INIS)

Wang Xizhang; Wu Qiang; Hu Zheng; Xu Hua; Miao Shui; Chen Yi

2000-01-01

A multifunctional apparatus for microwave plasma reaction has been set up, which can be used in the fields such as chemical synthesis, surface modification, and heterogeneous catalysis. The apparatus has laid an experimental foundation for new methods, new technologies, and new train of thoughts to be explored

Catalysis in electrochemistry: from fundamentals to strategies for fuel cell development

National Research Council Canada - National Science Library

Santos, Elizabeth; Schmickler, Wolfgang

2011-01-01

"Catalysis in Electrochemistry: From Fundamentals to Strategies for Fuel Cell Development is a modern, comprehensive reference work on catalysis in electrochemistry, including principles, methods, strategies, and applications...

Pollution Control by Catalysis

DEFF Research Database (Denmark)

Eriksen, Kim Michael; Fehrmann, Rasmus

1998-01-01

The report summarises the results of two years of collaboration supported by INTAS between Department of Chemistry,DTU,DK , IUSTI,Universite de Provence,FR, ICE/HT University 6of Patras,GR, and Boreskov Institute of Catalysis,RU.The project has been concerned with mechanistic studies of deNOx and...

Glutathione transferase mimics : Micellar catalysis of an enzymic reaction

NARCIS (Netherlands)

Lindkvist, Björn; Weinander, Rolf; Engman, Lars; Koetse, Marc; Engberts, Jan B.F.N.; Morgenstern, Ralf

1997-01-01

Substances that mimic the enzyme action of glutathione transferases (which serve in detoxification) are described. These micellar catalysts enhance the reaction rate between thiols and activated halogenated nitroarenes as well as alpha,beta-unsaturated carbonyls. The nucleophilic aromatic

CO chemistry/research trends in CO chemistry in the US

Energy Technology Data Exchange (ETDEWEB)

Cantacuzene, M

1978-10-01

Research trends in CO chemistry in the U.S. include the development of stable and selective homogeneous catalysts which would facilitate the removal of the heat of reaction and be resistant to sulfur poisoning for the methanation reaction, methanol synthesis, and Fischer-Tropsch synthesis; development of low-temperature homogeneous water gas shift catalysts; and research on the coordination chemistry and photochemical conversions of CO/sub 2/. In 1977, the National Science Foundation awarded 16 contracts for a total of $720,000 to promote the research in this field, including studies on chemisorption and heterogeneous catalysis (four contracts) and on transition metal complexes (ten contracts, of which seven are dedicated to metal clusters). Carbon monoxide-based processes, including water gas shift reactions, CO reduction to alkanes and alcohols, hydroformylation, and homogeneous carbonylation processes, recently developed in the U.S. are listed.

Process spectroscopy in microemulsions—setup and multi-spectral approach for reaction monitoring of a homogeneous hydroformylation process

Science.gov (United States)

Meyer, K.; Ruiken, J.-P.; Illner, M.; Paul, A.; Müller, D.; Esche, E.; Wozny, G.; Maiwald, M.

2017-03-01

Reaction monitoring in disperse systems, such as emulsions, is of significant technical importance in various disciplines like biotechnological engineering, chemical industry, food science, and a growing number other technical fields. These systems pose several challenges when it comes to process analytics, such as heterogeneity of mixtures, changes in optical behavior, and low optical activity. Concerning this, online nuclear magnetic resonance (NMR) spectroscopy is a powerful technique for process monitoring in complex reaction mixtures due to its unique direct comparison abilities, while at the same time being non-invasive and independent of optical properties of the sample. In this study the applicability of online-spectroscopic methods on the homogeneously catalyzed hydroformylation system of 1-dodecene to tridecanal is investigated, which is operated in a mini-plant scale at Technische Universität Berlin. The design of a laboratory setup for process-like calibration experiments is presented, including a 500 MHz online NMR spectrometer, a benchtop NMR device with 43 MHz proton frequency as well as two Raman probes and a flow cell assembly for an ultraviolet and visible light (UV/VIS) spectrometer. Results of high-resolution online NMR spectroscopy are shown and technical as well as process-specific problems observed during the measurements are discussed.

The nature of the active site in heterogeneous metal catalysis

DEFF Research Database (Denmark)

Nørskov, Jens Kehlet; Bligaard, Thomas; Larsen, Britt Hvolbæk

2008-01-01

This tutorial review, of relevance for the surface science and heterogeneous catalysis communities, provides a molecular-level discussion of the nature of the active sites in metal catalysis. Fundamental concepts such as "Bronsted-Evans-Polanyi relations'' and "volcano curves'' are introduced...

Plasmon-driven sequential chemical reactions in an aqueous environment.

Science.gov (United States)

Zhang, Xin; Wang, Peijie; Zhang, Zhenglong; Fang, Yurui; Sun, Mengtao

2014-06-24

Plasmon-driven sequential chemical reactions were successfully realized in an aqueous environment. In an electrochemical environment, sequential chemical reactions were driven by an applied potential and laser irradiation. Furthermore, the rate of the chemical reaction was controlled via pH, which provides indirect evidence that the hot electrons generated from plasmon decay play an important role in plasmon-driven chemical reactions. In acidic conditions, the hot electrons were captured by the abundant H(+) in the aqueous environment, which prevented the chemical reaction. The developed plasmon-driven chemical reactions in an aqueous environment will significantly expand the applications of plasmon chemistry and may provide a promising avenue for green chemistry using plasmon catalysis in aqueous environments under irradiation by sunlight.

Special section on Nano-Catalysis

CSIR Research Space (South Africa)

Makgwane, PR

2013-01-01

Full Text Available to achieve sustainable and green catalytic processes. The special issue contains 40 peer reviewed scientific papers that include four comprehensive review articles contributions from the invited experts in the respective catalysis fields....

Homogenization and dimension reduction of filtration combustion in heterogeneous thin layers

NARCIS (Netherlands)

Fatima, T.; Ijioma, E.R.; Ogawa, T.; Muntean, A.

2014-01-01

We study the homogenization of a reaction-diffusion-convection system posed in an e-periodic d-thin layer made of a two-component (solid-air) composite material. The microscopic system includes heat flow, diffusion and convection coupled with a nonlinear surface chemical reaction. We treat two

Francois Garin: Pioneer work in catalysis through synchrotron radiation

International Nuclear Information System (INIS)

Bazin, Dominique

2014-01-01

Starting from the late seventies, the progressively increased availability of beamlines dedicated to X-ray absorption spectroscopy allowed the execution of experiments in chemistry. In this manuscript, I describe the contribution of Francois Garin at the frontier of heterogeneous catalysis and synchrotron radiation. Working at LURE as a scientific in charge of a beamline dedicated to X-ray absorption spectroscopy during almost twenty years and thus, having the opportunity to discuss with research groups working in heterogeneous catalysis in Europe as well as in the United States, it was quite easy to show that his work is clearly at the origin of current research in heterogeneous catalysis, not only in France, but in different synchrotron radiation centres. (authors)

Spectroscopy in catalysis : an introduction

NARCIS (Netherlands)

Niemantsverdriet, J.W.

2000-01-01

Spectroscopy in Catalysis describes the most important modern analytical techniques used to investigate catalytic surfaces. These include electron spectroscopy (XPS, UPS, AES, EELS), ion spectroscopy (SIMS, SNMS, RBS, LEIS), vibrational spectroscopy (infrared, Raman, EELS), temperature-programmed

Heterogeneous catalysis at nanoscale for energy applications

CERN Document Server

Tao, Franklin (Feng); Kamat, Prashant V

2015-01-01

This book presents both the fundamentals concepts and latest achievements of a field that is growing in importance since it represents a possible solution for global energy problems.  It focuses on an atomic-level understanding of heterogeneous catalysis involved in important energy conversion processes. It presents a concise picture for the entire area of heterogeneous catalysis with vision at the atomic- and nano- scales, from synthesis, ex-situ and in-situ characterization, catalytic activity and selectivity, to mechanistic understanding based on experimental exploration and theoretical si

A simple fast microwave-assisted synthesis of thermoelectric bismuth telluride nanoparticles from homogeneous reaction-mixture

Energy Technology Data Exchange (ETDEWEB)

Pradhan, Susmita [Jadavpur University, Department of Instrumentation Science (India); Das, Rashmita [Jadavpur University, Department of Instrumentation and Electronics Engineering (India); Bhar, Radhaballabh [Jadavpur University, Department of Instrumentation Science (India); Bandyopadhyay, Rajib [Jadavpur University, Department of Instrumentation and Electronics Engineering (India); Pramanik, Panchanan, E-mail: pramanik1946@gmail.com [GLA University, Department of Chemistry and Nanoscience (India)

2017-02-15

A new simple chemical method for synthesis of nanocrystalline bismuth telluride (Bi{sub 2}Te{sub 3}) has been developed by microwave assisted reduction of homogeneous tartrate complexes of bismuth and tellurium metal ions with hydrazine. The reaction is performed at pH 10. The nano-crystallites have rhombohedral phase identified by XRD. The size distribution of nanoparticle is narrow and it ranges between 50 to 70 nm. FESEM shows that the fine powders are composed of small crystallites. The TEM micrographs show mostly deformed spherical particles and the lattice fringes are found to be 0.137 nm. Energy dispersive X-ray spectroscopy (EDX) analysis shows the atomic composition ratio between bismuth and tellurium is 2:3. Thermoelectric properties of the materials are studied after sintering by spark plasma sintering method (SPS). The grain size of the material after sintering is in the nanometer range. The material shows enhanced Seebeck coefficient and electrical conductivity value at 300 K. The figure of merit is found to be 1.18 at 300 K.

Enhancing Activity for the Oxygen Evolution Reaction

DEFF Research Database (Denmark)

Frydendal, Rasmus; Busch, Michael; Halck, Niels Bendtsen

2014-01-01

Electrochemical production of hydrogen, facilitated in electrolyzers, holds great promise for energy storage and solar fuel production. A bottleneck in the process is the catalysis of the oxygen evolution reaction, involving the transfer of four electrons. The challenge is that the binding energies...... of all reaction intermediates cannot be optimized individually. However, experimental investigations have shown that drastic improvements can be realized for manganese and cobalt-based oxides if gold is added to the surface or used as substrate. We propose an explanation for these enhancements based...... that the oxygen evolution reaction overpotential decreases by 100–300 mV for manganese oxides and 100 mV for cobalt oxides....

NATO Advanced Research Workshop on Frontiers in Polymerization Catalysis and Polymer Synthesis

CERN Document Server

Guyot, A

1987-01-01

Due to their specific properties, polymers with well-defined structures have been receiving increasing attention over the last several years. Owing to the wide variability of their properties, these specialty polymers have been used in various areas from biomedical engineering to electronics or energy applications. The synthesis of such polymers necessi­ tates the use of new methods of polymerization which derived from an insight into the mechanism of polymerization reactions. A NATO Advanced Research Workshop on "Frontiers in Polymerization Catalysis and Polymer Synthesis" was held in BANDOl (FRANCE) in February 1987. Its aim was to assess the new polymerization methods, as well as the latest advances in the mechanisms of conventional polymerization reactions together with their applications to the synthesis of new macromolecular structures. The financial support from the NATO Scientific Affairs Division which covered the "lecturers' accomodation and travel expenses as well as the organization charges of th...

Generating carbyne equivalents with photoredox catalysis

Science.gov (United States)

Wang, Zhaofeng; Herraiz, Ana G.; Del Hoyo, Ana M.; Suero, Marcos G.

2018-02-01

Carbon has the unique ability to bind four atoms and form stable tetravalent structures that are prevalent in nature. The lack of one or two valences leads to a set of species—carbocations, carbanions, radicals and carbenes—that is fundamental to our understanding of chemical reactivity. In contrast, the carbyne—a monovalent carbon with three non-bonded electrons—is a relatively unexplored reactive intermediate; the design of reactions involving a carbyne is limited by challenges associated with controlling its extreme reactivity and the lack of efficient sources. Given the innate ability of carbynes to form three new covalent bonds sequentially, we anticipated that a catalytic method of generating carbynes or related stabilized species would allow what we term an ‘assembly point’ disconnection approach for the construction of chiral centres. Here we describe a catalytic strategy that generates diazomethyl radicals as direct equivalents of carbyne species using visible-light photoredox catalysis. The ability of these carbyne equivalents to induce site-selective carbon-hydrogen bond cleavage in aromatic rings enables a useful diazomethylation reaction, which underpins sequencing control for the late-stage assembly-point functionalization of medically relevant agents. Our strategy provides an efficient route to libraries of potentially bioactive molecules through the installation of tailored chiral centres at carbon-hydrogen bonds, while complementing current translational late-stage functionalization processes. Furthermore, we exploit the dual radical and carbene character of the generated carbyne equivalent in the direct transformation of abundant chemical feedstocks into valuable chiral molecules.

Nanocomposite catalyst with palladium nanoparticles encapsulated in a polymeric acid: A model for tandem environmental catalysis

KAUST Repository

Isimjan, Tayirjan T.

2013-04-01

The synthesis and characterization of a novel hybrid nanocomposite catalyst comprised of palladium nanoparticles embedded in polystyrene sulfonic acid (PSSH) and supported on metal oxides is reported. The catalysts are intended for application in green catalysis, and they are shown to be effective in the hydrolysisreduction sequence of tandem catalytic reactions required for conversion of 2-phenyl-1,3-dioxolane to toluene or of phenol to cyclohexane. The two distinct components in the catalyst, Pd nanoparticles and acidic PSSH, are capable of catalyzing sequential reactions in one pot under mild conditions. This work has demonstrated a powerful approach toward designing highperformance, multifunctional, scalable, and environmentally friendly nanostructured tandem catalysts. © 2013 American Chemical Society.

Regioselectivity and Enantioselectivity in Nickel-Catalysed Reductive Coupling Reactions of Alkynes

Science.gov (United States)

Moslin, Ryan M.; Miller-Moslin, Karen; Jamison, Timothy F.

2011-01-01

Nickel-catalysed reductive coupling reactions of alkynes have emerged as powerful synthetic tools for the selective preparation of functionalized alkenes. One of the greatest challenges associated with these transformations is control of regioselectivity. Recent work from our laboratory has provided an improved understanding of several of the factors governing regioselectivity in these reactions, and related studies have revealed that the reaction mechanism can differ substantially depending on the ligand employed. A discussion of stereoselective transformations and novel applications of nickel catalysis in coupling reactions of alkynes is also included. PMID:17971951

Electrostatic Self-Assembly of Au Nanoparticles onto Thermosensitive Magnetic Core-Shell Microgels for Thermally Tunable and Magnetically Recyclable Catalysis.

Science.gov (United States)

Liu, Guoqiang; Wang, Daoai; Zhou, Feng; Liu, Weimin

2015-06-01

A facile route to fabricate a nanocomposite of Fe3O4@poly[N-isopropylacrylamide (NIPAM)-co-2-(dimethylamino)ethyl methacrylate (DMAEMA)]@Au (Fe3O4@PND@Au) is developed for magnetically recyclable and thermally tunable catalysis. The negatively charged Au nanoparticles with an average diameter of 10 nm are homogeneously loaded onto positively charged thermoresponsive magnetic core-shell microgels of Fe3O4@poly(NIPAM-co-DMAEMA) (Fe3O4@PND) through electrostatic self-assembly. This type of attachment offers perspectives for using charged polymeric shell on a broad variety of nanoparticles to immobilize the opposite-charged nanoparticles. The thermosensitive PND shell with swollen or collapsed properties can be as a retractable Au carrier, thereby tuning the aggregation or dispersion of Au nanoparticles, which leads to an increase or decrease of catalytic activity. Therefore, the catalytic activity of Fe3O4@PND@Au can be modulated by the volume transition of thermosensitive microgel shells. Importantly, the mode of tuning the aggregation or dispersion of Au nanoparticles using a thermosensitive carrier offers a novel strategy to adjust and control the catalytic activity, which is completely different with the traditional regulation mode of controlling the diffusion of reactants toward the catalytic Au core using the thermosensitive poly(N-isopropylacrylamide) network as a nanogate. Concurrent with the thermally tunable catalysis, the magnetic susceptibility of magnetic cores enables the Fe3O4@PND@Au nanocomposites to be capable of serving as smart nanoreactors for thermally tunable and magnetically recyclable catalysis. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cu and Cu-Based Nanoparticles: Synthesis and Applications in Catalysis.

Science.gov (United States)

Gawande, Manoj B; Goswami, Anandarup; Felpin, François-Xavier; Asefa, Tewodros; Huang, Xiaoxi; Silva, Rafael; Zou, Xiaoxin; Zboril, Radek; Varma, Rajender S

2016-03-23

The applications of copper (Cu) and Cu-based nanoparticles, which are based on the earth-abundant and inexpensive copper metal, have generated a great deal of interest in recent years, especially in the field of catalysis. The possible modification of the chemical and physical properties of these nanoparticles using different synthetic strategies and conditions and/or via postsynthetic chemical treatments has been largely responsible for the rapid growth of interest in these nanomaterials and their applications in catalysis. In addition, the design and development of novel support and/or multimetallic systems (e.g., alloys, etc.) has also made significant contributions to the field. In this comprehensive review, we report different synthetic approaches to Cu and Cu-based nanoparticles (metallic copper, copper oxides, and hybrid copper nanostructures) and copper nanoparticles immobilized into or supported on various support materials (SiO2, magnetic support materials, etc.), along with their applications in catalysis. The synthesis part discusses numerous preparative protocols for Cu and Cu-based nanoparticles, whereas the application sections describe their utility as catalysts, including electrocatalysis, photocatalysis, and gas-phase catalysis. We believe this critical appraisal will provide necessary background information to further advance the applications of Cu-based nanostructured materials in catalysis.

Catalyst synthesis and evaluation using an integrated atomic layer deposition synthesis–catalysis testing tool

International Nuclear Information System (INIS)

Camacho-Bunquin, Jeffrey; Shou, Heng; Marshall, Christopher L.; Aich, Payoli; Beaulieu, David R.; Klotzsch, Helmut; Bachman, Stephen; Hock, Adam; Stair, Peter

2015-01-01

An integrated atomic layer deposition synthesis-catalysis (I-ALD-CAT) tool was developed. It combines an ALD manifold in-line with a plug-flow reactor system for the synthesis of supported catalytic materials by ALD and immediate evaluation of catalyst reactivity using gas-phase probe reactions. The I-ALD-CAT delivery system consists of 12 different metal ALD precursor channels, 4 oxidizing or reducing agents, and 4 catalytic reaction feeds to either of the two plug-flow reactors. The system can employ reactor pressures and temperatures in the range of 10 −3 to 1 bar and 300–1000 K, respectively. The instrument is also equipped with a gas chromatograph and a mass spectrometer unit for the detection and quantification of volatile species from ALD and catalytic reactions. In this report, we demonstrate the use of the I-ALD-CAT tool for the synthesis of platinum active sites and Al 2 O 3 overcoats, and evaluation of catalyst propylene hydrogenation activity

Catalyst synthesis and evaluation using an integrated atomic layer deposition synthesis–catalysis testing tool

Energy Technology Data Exchange (ETDEWEB)

Camacho-Bunquin, Jeffrey; Shou, Heng; Marshall, Christopher L. [Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439 (United States); Aich, Payoli [Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439 (United States); Department of Chemical Engineering, University of Illinois at Chicago, Chicago, Illinois 60607 (United States); Beaulieu, David R.; Klotzsch, Helmut; Bachman, Stephen [Arradiance Inc., Sudbury, Massachusetts 01776 (United States); Hock, Adam [Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439 (United States); Department of Chemistry, Illinois Institute of Technology, Chicago, Illinois 60616 (United States); Stair, Peter [Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439 (United States); Department of Chemistry, Northwestern University, Evanston, Illinois 60208 (United States)

2015-08-15

An integrated atomic layer deposition synthesis-catalysis (I-ALD-CAT) tool was developed. It combines an ALD manifold in-line with a plug-flow reactor system for the synthesis of supported catalytic materials by ALD and immediate evaluation of catalyst reactivity using gas-phase probe reactions. The I-ALD-CAT delivery system consists of 12 different metal ALD precursor channels, 4 oxidizing or reducing agents, and 4 catalytic reaction feeds to either of the two plug-flow reactors. The system can employ reactor pressures and temperatures in the range of 10{sup −3} to 1 bar and 300–1000 K, respectively. The instrument is also equipped with a gas chromatograph and a mass spectrometer unit for the detection and quantification of volatile species from ALD and catalytic reactions. In this report, we demonstrate the use of the I-ALD-CAT tool for the synthesis of platinum active sites and Al{sub 2}O{sub 3} overcoats, and evaluation of catalyst propylene hydrogenation activity.

Catalysis by metal-organic frameworks: fundamentals and opportunities.

Science.gov (United States)

Ranocchiari, Marco; van Bokhoven, Jeroen Anton

2011-04-14

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

Approaches to single-nanoparticle catalysis.

Science.gov (United States)

Sambur, Justin B; Chen, Peng

2014-01-01

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

Consequences of acid strength for isomerization and elimination catalysis on solid acids.

Science.gov (United States)

Macht, Josef; Carr, Robert T; Iglesia, Enrique

2009-05-13

We address here the manner in which acid catalysis senses the strength of solid acids. Acid strengths for Keggin polyoxometalate (POM) clusters and zeolites, chosen because of their accurately known structures, are described rigorously by their deprotonation energies (DPE). Mechanistic interpretations of the measured dynamics of alkane isomerization and alkanol dehydration are used to obtain rate and equilibrium constants and energies for intermediates and transition states and to relate them to acid strength. n-Hexane isomerization rates were limited by isomerization of alkoxide intermediates on bifunctional metal-acid mixtures designed to maintain alkane-alkene equilibrium. Isomerization rate constants were normalized by the number of accessible protons, measured by titration with 2,6-di-tert-butylpyridine during catalysis. Equilibrium constants for alkoxides formed by protonation of n-hexene increased slightly with deprotonation energies (DPE), while isomerization rate constants decreased and activation barriers increased with increasing DPE, as also shown for alkanol dehydration reactions. These trends are consistent with thermochemical analyses of the transition states involved in isomerization and elimination steps. For all reactions, barriers increased by less than the concomitant increase in DPE upon changes in composition, because electrostatic stabilization of ion-pairs at the relevant transition states becomes more effective for weaker acids, as a result of their higher charge density at the anionic conjugate base. Alkoxide isomerization barriers were more sensitive to DPE than for elimination from H-bonded alkanols, the step that limits 2-butanol and 1-butanol dehydration rates; the latter two reactions showed similar DPE sensitivities, despite significant differences in their rates and activation barriers, indicating that slower reactions are not necessarily more sensitive to acid strength, but instead reflect the involvement of more unstable organic

Supported Ionic Liquid Phase (SILP) Catalysis for the Production of Acetic acid by Methanol Carbonylation

DEFF Research Database (Denmark)

Hanning, Christopher William

at the beginning with the construction of a suitable test reactor, then followed by the synthesis and testing of all the catalysts reported. A variety of nitrogen based ionic liquids were initially tested, giving good results and stability in the system. Later a number of phosphonium based salts were tested (these......The work presented here is focused on the development of a new reaction process. It applies Supported Ionic Liquid Phase (SILP) catalysis to a specific reaction. By reacting methanol and carbon monoxide over a rhodium catalyst, acetic acid can be formed. This reaction is important on a large scale...... were no longer classified as ionic liquids due to melting points above 100◦C). The phosphonium salts showed even better activity in the system compared to the ionic liquids. Overall the work has shown that this process for the manufacture of acetic acid is viable industrially. This is backed up...

Asymmetric Aldol Additions: A Guided-Inquiry Laboratory Activity on Catalysis

Science.gov (United States)

King, Jorge H. Torres; Wang, Hong; Yezierski, Ellen J.

2018-01-01

Despite the importance of asymmetric catalysis in both the pharmaceutical and commodity chemicals industries, asymmetric catalysis is under-represented in undergraduate chemistry laboratory curricula. A novel guided-inquiry experiment based on the asymmetric aldol addition was developed. Students conduct lab work to compare the effectiveness of…

Identifying systematic DFT errors in catalytic reactions

DEFF Research Database (Denmark)

Christensen, Rune; Hansen, Heine Anton; Vegge, Tejs

2015-01-01

Using CO2 reduction reactions as examples, we present a widely applicable method for identifying the main source of errors in density functional theory (DFT) calculations. The method has broad applications for error correction in DFT calculations in general, as it relies on the dependence...... of the applied exchange–correlation functional on the reaction energies rather than on errors versus the experimental data. As a result, improved energy corrections can now be determined for both gas phase and adsorbed reaction species, particularly interesting within heterogeneous catalysis. We show...... that for the CO2 reduction reactions, the main source of error is associated with the C[double bond, length as m-dash]O bonds and not the typically energy corrected OCO backbone....

2-Diazo-1-phenyl-2-((trifluoromethyl)sulfonyl)ethan-1-one: Another Utility for Electrophilic Trifluoromethylthiolation Reactions.

Science.gov (United States)

Huang, Zhongyan; Okuyama, Kenta; Wang, Chen; Tokunaga, Etsuko; Li, Xiaorui; Shibata, Norio

2016-06-01

2-Diazo-1-phenyl-2-((trifluoromethyl)sulfonyl)ethan-1-one (diazo-triflone) ( 2 ) is not only a building block but also a reagent. In this study, diazo-triflone, which was originally used for the synthesis of β-lactam triflones as a trifluoromethanesulfonyl (SO 2 CF 3 ) building block under catalyst-free thermal conditions, is redisclosed as an effective electrophilic trifluoromethylthiolation reagent under copper catalysis. A broad set of enamines, indoles, β-keto esters, pyrroles, and anilines were nicely transformed into corresponding trifluoromethylthio (SCF 3 ) compounds in good to high yields by diazo-triflone under copper catalysis via an electrophilic-type reaction. A coupling-type trifluoromethylthiolation reaction of aryl iodides was also realized by diazo-triflone in acceptable yields.

Dinuclear Tetrapyrazolyl Palladium Complexes Exhibiting Facile Tandem Transfer Hydrogenation/Suzuki Coupling Reaction of Fluoroarylketone

KAUST Repository

Dehury, Niranjan; Maity, Niladri; Tripathy, Suman Kumar; Basset, Jean-Marie; Patra, Srikanta

2016-01-01

Herein, we report an unprecedented example of dinuclear pyrazolyl-based Pd complexes exhibiting facile tandem catalysis for fluoroarylketone: Tetrapyrazolyl di-palladium complexes with varying Pd-Pd distances efficiently catalyze the tandem reaction

Catalyzed oxidation reactions. IV. Picolinic acid catalysis of chromic acid oxidations

International Nuclear Information System (INIS)

Rocek, J.; Peng, T.Y.

1977-01-01

Picolinic acid and several closely related acids are effective catalysts in the chromic acid oxidation of primary and secondary alcohols; the oxidation of other substrates is accelerated only moderately. The reaction is first order in chromium-(VI), alcohol, and picolinic acid; it is second order in hydrogen ions at low acidity and approaches acidity independence at high perchloric acid concentrations. A primary deuterium kinetic isotope effect is observed at high but not at low acidities. At low acidity the reaction has a considerably lower activation energy and more negative activation entropy than at higher acidities. The reactive intermediate in the proposed mechanism is a negatively charged termolecular complex formed from chromic acid, picolinic acid, and alcohol. The rate-limiting step of the reaction changes with the acidity of the solution. At higher acidities the intermediate termolecular complex is formed reversibly and the overall reaction rate is determined by the rate of its decomposition into reaction products; at low acidities the formation of the complex is irreversible and hence rate limiting. Picolinic acids with a substituent in the 6 position show a greatly reduced catalytic activity. This observation is interpreted as suggesting a square pyramidal or octahedral structure for the reactive chromium (VI) intermediate. The temperature dependence of the deuterium isotope effect has been determined and the significance of the observed large values for E/sub a//sup D/ - E/sub a//sup H/ and A/sup D//A/sup H/ is discussed

3. International conference on catalysis in membrane reactors

Energy Technology Data Exchange (ETDEWEB)

NONE

1998-09-01

The 3. International Conference on Catalysis in Membrane Reactors, Copenhagen, Denmark, is a continuation of the previous conferences held in Villeurbanne 1994 and Moscow 1996 and will deal with the rapid developments taking place within membranes with emphasis on membrane catalysis. The approx. 80 contributions in form of plenary lectures and posters discuss hydrogen production, methane reforming into syngas, selectivity and specificity of various membranes etc. The conference is organised by the Danish Catalytic Society under the Danish Society for Chemical Engineering. (EG)

Scandium(III) catalysis of transimination reactions. Independent and constitutionally coupled reversible processes.

Science.gov (United States)

Giuseppone, Nicolas; Schmitt, Jean-Louis; Schwartz, Evan; Lehn, Jean-Marie

2005-04-20

Sc(OTf)(3) efficiently catalyzes the self-sufficient transimination reaction between various types of C=N bonds in organic solvents, with turnover frequencies up to 3600 h(-)(1) and rate accelerations up to 6 x 10(5). The mechanism of the crossover reaction in mixtures of amines and imines is studied, comparing parallel individual reactions with coupled equilibria. The intrinsic kinetic parameters for isolated reactions cannot simply be added up when several components are mixed, and the behavior of the system agrees with the presence of a unique mediator that constitutes the core of a network of competing reactions. In mixed systems, every single amine or imine competes for the same central hub, in accordance with their binding affinity for the catalyst metal ion center. More generally, the study extends the basic principles of constitutional dynamic chemistry to interconnected chemical transformations and provides a step toward dynamic systems of increasing complexity.

A Novel and Efficient Five-Component Synthesis of Pyrazole Based Pyrido[2,3-d]pyrimidine-diones in Water: A Triply Green Synthesis

Directory of Open Access Journals (Sweden)

Majid M. Heravi

2016-04-01

Full Text Available A novel one pot synthesis of pyrazolo[4′,3′:5,6]pyrido[2,3-d]pyrimidine-diones, via a five-component reaction, involving, hydrazine hydrate, ethyl acetoacetate, and 1,3-dimethyl barbituric acid, an appropriate aryl aldehydes and ammonium acetate catalyzed via both of heterogeneous and homogeneous catalysis in water, is reported.

Penicillin Hydrolysis: A Kinetic Study of a Multistep, Multiproduct Reaction.

Science.gov (United States)

McCarrick, Thomas A.; McLafferty, Fred W.

1984-01-01

Background, procedures used, and typical results are provided for an experiment in which students carry out the necessary measurements on the acid-catalysis of penicillin in two hours. By applying kinetic theory to the data obtained, the reaction pathways for the hydrolysis of potassium benzyl penicillin are elucidated. (JN)

Propan-1-ol Oxidation Reaction on Au/TiO2 Catalysts

African Journals Online (AJOL)

MBI

2014-11-27

Nov 27, 2014 ... a decomposition pathway, producing CO2 and H2O. However, the presence of gold ... complete oxidation reaction of propan-1-ol on the catalysts. Keywords: Gold Catalysis ... flowed at a rate of 30 mL min-1. Propan- o-l was.

Homogenization technique for strongly heterogeneous zones in research reactors

International Nuclear Information System (INIS)

Lee, J.T.; Lee, B.H.; Cho, N.Z.; Oh, S.K.

1991-01-01

This paper reports on an iterative homogenization method using transport theory in a one-dimensional cylindrical cell model developed to improve the homogenized cross sections fro strongly heterogeneous zones in research reactors. The flux-weighting homogenized cross sections are modified by a correction factor, the cell flux ratio under an albedo boundary condition. The albedo at the cell boundary is iteratively determined to reflect the geometry effects of the material properties of the adjacent cells. This method has been tested with a simplified core model of the Korea Multipurpose Research Reactor. The results demonstrate that the reaction rates of an off-center control shroud cell, the multiplication factor, and the power distribution of the reactor core are close to those of the fine-mesh heterogeneous transport model

Shape-selective synthesis of Sn(MoO4)2 nanomaterials for catalysis and supercapacitor applications.

Science.gov (United States)

Sakthikumar, K; Ede, Sivasankara Rao; Mishra, Soumyaranjan; Kundu, Subrata

2016-06-07

Size and shape-selective Sn(MoO4)2 nanomaterials have been synthesized for the first time using a simple hydrothermal route by the reaction of Sn(ii) chloride salt with sodium molybdate in CTAB micellar media under stirring at 60 °C temperature for about three hours. Needle-like and flake-like Sn(MoO4)2 nanomaterials were synthesized by optimizing the CTAB to metal salt molar ratio and by controlling other reaction parameters. The eventual diameter and length of the nanoneedles are ∼100 ± 10 nm and ∼850 ± 100 nm respectively. The average diameter of the flakes is ∼250 ± 50 nm. The synthesized Sn(MoO4)2 nanomaterials can be used in two potential applications, namely, catalytic reduction of nitroarenes and as an anodic material in electrochemical supercapacitors. From the catalysis study, it was observed that the Sn(MoO4)2 nanomaterials could act as a potential catalyst for the successful photochemical reduction of nitroarenes into their respective aminoarenes within a short reaction time. From the supercapacitor study, it was observed that the Sn(MoO4)2 nanomaterials of different shapes show different specific capacitance (Cs) values and the highest Cs value was observed for Sn(MoO4)2 nanomaterials having a flake-like morphology. The highest Cs value observed was 109 F g(-1) at a scan rate of 5 mV s(-1) for the flake-like Sn(MoO4)2 nanomaterials. The capacitor shows an excellent long cycle life along with 70% retention of the Cs value, even after 4000 consecutive cycles at a current density of 8 mA cm(-2). Other than the applications in catalysis and supercapacitors, the synthesized nanomaterials can find further applications in photoluminescence, sensor and other energy-related devices.

Long-lived CO/sub 2/ lasers with distributed heterogeneous catalysis

Energy Technology Data Exchange (ETDEWEB)

Browne, P G; Smith, A L.S.

1974-12-11

In a sealed CO/sub 2/-N/sub 2/-He system with a clean discharge tube the degree of dissociation of the CO/sub 2/ is greater than 80 percent (with no hydrogen present), and laser action cannot be obtained. If Pt is distributed along the discharge tube walls as a discontinuous film it catalyses back-reactions reforming CO/sub 2/. The degree of dissociation is then less than 40 percent, and efficient laser action at 10.6 ..mu.. is obtained. Using such distributed heterogeneous catalysis, a CO/sub 2/-N/sub 2/-He-Xe laser has operated for more than 3000 h. In this system, both H/sub 2/ and D/sub 2/ are undesirable additives because they decrease the excitation rate of the upper laser level. (auth)

Signal-enhanced electrochemiluminescence immunosensor based on synergistic catalysis of nicotinamide adenine dinucleotide hydride and silver nanoparticles.

Science.gov (United States)

Wang, Guangjie; Jin, Feng; Dai, Nan; Zhong, Zhaoyang; Qing, Yi; Li, Mengxia; Yuan, Ruo; Wang, Dong

2012-03-01

A new metal-organic nanocomposite with synergistic catalysis function was prepared and developed to construct an electrochemiluminescence (ECL) immunosensor for ultrasensitive detection of tumor biomarker CA125. Silver nanoparticles (AgNPs) and nicotinamide adenine dinucleotide hydride (NADH) that can participate and catalyze the ECL reaction of Ru(bpy)(3)(2+) were employed as the metal component and the organic component to synthesize the metal-organic nanocomposite of NADH-AgNPs (NA). The novel ECL immunosensor was assembled via Ru(bpy)(3)(2+)-doped silica nanoparticles (Ru-SiO(2)) modified electrode with the NA as immune labels. First, the chitosan-suspended Ru-SiO(2) nanoparticles were cast on the gold electrode surface to immobilize the ECL probes of Ru(bpy)(3)(2+) and link gold nanoparticles. Then, the primary antibodies were loaded onto the modified electrode via the gold sulfhydryl covalent binding. After immunobinding the analytes of antigen, NA-attached secondary antibodies could be captured as a sandwich type on the electrode. Finally, based on the circularly synergistic catalysis by the silver and NADH for the solid-phase ECL of Ru(bpy)(3)(2+), the proposed immunosensor sensed the concentration of antigen. The synergistic ECL catalysis of metal-organic nanocomposite amplified response signal and pushed the detection limit down to 0.03 U ml(-1), which initiated a new ECL labeling field and has great significance for ECL immunoassays. Copyright © 2012 Elsevier Inc. All rights reserved.

Homogenization of a thermo-diffusion system with Smoluchowski interactions

NARCIS (Netherlands)

Krehel, O.; Aiki, T.; Muntean, A.

2014-01-01

We study the solvability and homogenization of a thermal-diffusion reaction problem posed in a periodically perforated domain. The system describes the motion of populations of hot colloidal particles interacting together via Smoluchowski production terms. The upscaled system, obtained via two-scale

Electrochemical immunoassay for thyroxine detection using cascade catalysis as signal amplified enhancer and multi-functionalized magnetic graphene sphere as signal tag

Energy Technology Data Exchange (ETDEWEB)

Han, Jing; Zhuo, Ying, E-mail: yingzhuo@swu.edu.cn; Chai, Yaqin; Yu, Yanqing; Liao, Ni; Yuan, Ruo, E-mail: yuanruo@swu.edu.cn

2013-08-06

Graphical abstract: -- Highlights: •A reusable electrochemical immunosensor is developed for thyroxine detection. •Cascade catalysis as signal amplified enhancer. •Multi-functionalized magnetic graphene sphere as signal tag. •The novel strategy has the advantages of high sensitivity, good selectivity and reproducibility. -- Abstract: This paper constructed a reusable electrochemical immunosensor for the detection of thyroxine at an ultralow concentration using cascade catalysis of cytochrome c (Cyt c) and glucose oxidase (GOx) as signal amplified enhancer. It is worth pointing out that numerous Cyt c and GOx were firstly carried onto the double-stranded DNA polymers based on hybridization chain reaction (HCR), and then the amplified responses could be achieved by cascade catalysis of Cyt c and GOx recycling with the help of glucose. Moreover, multi-functionalized magnetic graphene sphere was synthesized and used as signal tag, which not only exhibited good mechanical properties, large surface area and an excellent electron transfer rate of graphene, but also possessed excellent redox activity and desirable magnetic property. With a sandwich-type immunoreaction, the proposed cascade catalysis amplification strategy could greatly enhance the sensitivity for the detection of thyroxine. Under the optimal conditions, the immunosensor showed a wide linear ranged from 0.05 pg mL{sup −1} to 5 ng mL{sup −1} and a low detection limit down to 15 fg mL{sup −1}. Importantly, the proposed method offers promise for reproducible and cost-effective analysis of biological samples.

On the mechanism of hydrogen evolution catalysis by proteins: A case study with bovine serum albumin

Energy Technology Data Exchange (ETDEWEB)

Doneux, Th., E-mail: tdoneux@ulb.ac.b [Chimie Analytique et Chimie des Interfaces, Faculte des Sciences, Universite Libre de Bruxelles, Boulevard du Triomphe 2, CP 255, B-1050 Bruxelles (Belgium); Institute of Biophysics, Academy of Sciences of the Czech Republic, Kralovopolska 135, 612 65 Brno (Czech Republic); Ostatna, Veronika [Institute of Biophysics, Academy of Sciences of the Czech Republic, Kralovopolska 135, 612 65 Brno (Czech Republic); Palecek, Emil, E-mail: palecek@ibp.cz [Institute of Biophysics, Academy of Sciences of the Czech Republic, Kralovopolska 135, 612 65 Brno (Czech Republic)

2011-10-30

Highlights: > Proteins catalyse hydrogen evolution at mercury electrodes. > The adsorbed protein is the mediator and the buffer proton donor is the substrate. > The characteristics of the catalytic peak are connected to the protein properties. - Abstract: The catalysis of the hydrogen evolution reaction (HER) by proteins has been known for decades but was only recently found to be useful for electroanalytical purposes. The mechanism of the catalytic process is investigated at hanging mercury drop electrodes by cyclic voltammetry, with bovine serum albumin as a model system. It is shown that the catalyst is the protein in the adsorbed state. The influence of various parameters such as the accumulation time, scan rate or buffer concentration is studied, and interpreted in the framework of a surface catalytic mechanism. Under the experimental conditions used in the work, a 'total catalysis' phenomenon takes place, the rate of HER being limited by the diffusion of the proton donor. The adequacy of the existing models is discussed, leading to a call for the development of more refined models.

Curvature bound from gravitational catalysis

Science.gov (United States)

Gies, Holger; Martini, Riccardo

2018-04-01

We determine bounds on the curvature of local patches of spacetime from the requirement of intact long-range chiral symmetry. The bounds arise from a scale-dependent analysis of gravitational catalysis and its influence on the effective potential for the chiral order parameter, as induced by fermionic fluctuations on a curved spacetime with local hyperbolic properties. The bound is expressed in terms of the local curvature scalar measured in units of a gauge-invariant coarse-graining scale. We argue that any effective field theory of quantum gravity obeying this curvature bound is safe from chiral symmetry breaking through gravitational catalysis and thus compatible with the simultaneous existence of chiral fermions in the low-energy spectrum. With increasing number of dimensions, the curvature bound in terms of the hyperbolic scale parameter becomes stronger. Applying the curvature bound to the asymptotic safety scenario for quantum gravity in four spacetime dimensions translates into bounds on the matter content of particle physics models.

Ferroelectric based catalysis: Switchable surface chemistry

Science.gov (United States)

Kakekhani, Arvin; Ismail-Beigi, Sohrab

2015-03-01

We describe a new class of catalysts that uses an epitaxial monolayer of a transition metal oxide on a ferroelectric substrate. The ferroelectric polarization switches the surface chemistry between strongly adsorptive and strongly desorptive regimes, circumventing difficulties encountered on non-switchable catalytic surfaces where the Sabatier principle dictates a moderate surface-molecule interaction strength. This method is general and can, in principle, be applied to many reactions, and for each case the choice of the transition oxide monolayer can be optimized. Here, as a specific example, we show how simultaneous NOx direct decomposition (into N2 and O2) and CO oxidation can be achieved efficiently on CrO2 terminated PbTiO3, while circumventing oxygen (and sulfur) poisoning issues. One should note that NOx direct decomposition has been an open challenge in automotive emission control industry. Our method can expand the range of catalytically active elements to those which are not conventionally considered for catalysis and which are more economical, e.g., Cr (for NOx direct decomposition and CO oxidation) instead of canonical precious metal catalysts. Primary support from Toyota Motor Engineering and Manufacturing, North America, Inc.

Radiochemical synthesis of a carbon-supported Pt–SnO2 bicomponent nanostructure exhibiting enhanced catalysis of ethanol oxidation

International Nuclear Information System (INIS)

Okazaki, Tomohisa; Seino, Satoshi; Nakagawa, Takashi; Kugai, Junichiro; Ohkubo, Yuji; Akita, Tomoki; Nitani, Hiroaki; Yamamoto, Takao A.

2015-01-01

Carbon-supported Pt–SnO 2 electrocatalysts with various Sn/Pt molar ratios were prepared by an electron beam irradiation method. These catalysts were composed of metallic Pt particles approximately 5 nm in diameter together with low crystalline SnO 2 . The contact between the Pt and SnO 2 in these materials varied with the amount of dissolved oxygen in the precursor solutions and it was determined that intimate contact between the Pt and SnO 2 significantly enhanced the catalytic activity of these materials during the ethanol oxidation reaction. The mechanism by which the contact varies is discussed based on the radiochemical reduction process. - Highlights: • Ethanol oxidation catalysis was enhanced by Sn-addition, far less than ever reported. • Pt–SnO 2 contact is crucial to the catalysis enhancement, alloying of Sn is not necessary. • Nano-scaled intimate contact between Pt and SnO 2 was directly observed

ELECTROCHEMICAL PROMOTED CATALYSIS: TOWARDS PRACTICAL UTILIZATION

Directory of Open Access Journals (Sweden)

DIMITRIOS TSIPLAKIDES

2008-07-01

Full Text Available Electrochemical promotion (EP of catalysis has already been recognized as “a valuable development in catalytic research” (J. Pritchard, 1990 and as “one of the most remarkable advances in electrochemistry since 1950” (J. O’M. Bockris, 1996. Laboratory studies have clearly elucidated the phenomenology of electrochemical promotion and have proven that EP is a general phenomenon at the interface of catalysis and electrochemistry. The major progress toward practical utilization of EP is surveyed in this paper. The focus is given on the electropromotion of industrial ammonia synthesis catalyst, the bipolar EP and the development of a novel monolithic electropromoted reactor (MEPR in conjunction with the electropromotion of thin sputtered metal films. Future perspectives of electrochemical promotion applications in the field of hydrogen technologies are discussed.

Catalysis. Innovative applications in petrochemistry and refining. Preprints

Energy Technology Data Exchange (ETDEWEB)

Ernst, S.; Balfanz, U.; Jess, A.; Lercher, J.A.; Lichtscheidl, J.; Marchionna, M.; Nees, F.; Santacesaria, E. (eds.)

2011-07-01

Within the DGMK conference at 4th to 6th October, 2011 in Dresden (Federal Republic of Germany) the following lectures were held: (1) Developing linear-alpha-olefins technology - From laboratory to a commercial plant (A. Meiswinkel); (2) New developments in oxidation catalysis (F. Rosowski); (3) Study of the performance of vanadium based catalysts prepared by grafting in the oxidative dehydrogenation of propane (E. Santacesaria); (4) Hydrocracking for oriented conversion of heavy oils: recent trends for catalyst development (F. Bertoncini); (5) Acidic ionic liquids for n-alkane isomerization in a liquid-liquid or slurry-phase reaction mode (C. Meyer); (6) Dual catalyst system for the hydrocracking of heavy oils and residues (G. Bellussi); (7) Understanding hydrodenitrogenation on novel unsupported sulphide Mo-W-Ni catalysts (J. Hein); (8) Hydrocracking of ethyllaurate on bifunctional micro-/mesoporous composite materials (M. Adam); (9) Catalytic dehydration of ethanol to ethylene (Ying Zhu); (10) The Evonik-Uhde HPPO process for propylene oxide production (B. Jaeger); (11) A green two-step process for adipic acid production from cyclohexene: A study on parameters affecting selectivity (F. Cavani); (12) DISY: The direct synthesis of hydrogen peroxide, a bridge for innovative applications (R, Buzzoni); (13) Solid catalyst with ionic liquid layer (SCILL) - A concept to improve the selectivity of selective hydrogenations (A. Jess); (14) Co-Zn-Al based hydrotalcites as catalysts for Fischer-Tropsch process (C.L. Bianchi); (15) Honeycomb supports with high thermal conductivity for the Fischer-Tropsch synthesis (C.G. Visconti); (16) How to make Fischer-Tropsch catalyst scale-up fully reliable (L. Fischer); (17) New developments in FCC catalysis (C.P. Kelkar); (18) The potential of medium-pore zeolites for improved propene yields from catalytic cracking (F. Bager).

Compact reaction cell for homogenizing and down-blending highly enriched uranium metal

Science.gov (United States)

McLean, W. II; Miller, P.E.; Horton, J.A.

1995-05-02

The invention is a specialized reaction cell for converting uranium metal to uranium oxide. In a preferred form, the reaction cell comprises a reaction chamber with increasing diameter along its length (e.g. a cylindrical chamber having a diameter of about 2 inches in a lower portion and having a diameter of from about 4 to about 12 inches in an upper portion). Such dimensions are important to achieve the necessary conversion while at the same time affording criticality control and transportability of the cell and product. The reaction chamber further comprises an upper port and a lower port, the lower port allowing for the entry of reactant gases into the reaction chamber, the upper port allowing for the exit of gases from the reaction chamber. A diffuser plate is attached to the lower port of the reaction chamber and serves to shape the flow of gas into the reaction chamber. The reaction cell further comprises means for introducing gases into the reaction chamber and a heating means capable of heating the contents of the reaction chamber. The present invention also relates to a method for converting uranium metal to uranium oxide in the reaction cell of the present invention. The invention is useful for down-blending highly enriched uranium metal by the simultaneous conversion of highly enriched uranium metal and natural or depleted uranium metal to uranium oxide within the reaction cell. 4 figs.

Compact reaction cell for homogenizing and down-blanding highly enriched uranium metal

Science.gov (United States)

McLean, II, William; Miller, Philip E.; Horton, James A.

1995-01-01

The invention is a specialized reaction cell for converting uranium metal to uranium oxide. In a preferred form, the reaction cell comprises a reaction chamber with increasing diameter along its length (e.g. a cylindrical chamber having a diameter of about 2 inches in a lower portion and having a diameter of from about 4 to about 12 inches in an upper portion). Such dimensions are important to achieve the necessary conversion while at the same time affording criticality control and transportability of the cell and product. The reaction chamber further comprises an upper port and a lower port, the lower port allowing for the entry of reactant gasses into the reaction chamber, the upper port allowing for the exit of gasses from the reaction chamber. A diffuser plate is attached to the lower port of the reaction chamber and serves to shape the flow of gas into the reaction chamber. The reaction cell further comprises means for introducing gasses into the reaction chamber and a heating means capable of heating the contents of the reaction chamber. The present invention also relates to a method for converting uranium metal to uranium oxide in the reaction cell of the present invention. The invention is useful for down-blending highly enriched uranium metal by the simultaneous conversion of highly enriched uranium metal and natural or depleted uranium metal to uranium oxide within the reaction cell.

Magnetic nanoparticles of NiCuZn tested in different conditions in catalysis for biodiesel

International Nuclear Information System (INIS)

Dantas, J.; Silva, F.N.; Silva, A.S.; Pereira, K.R.O.; Costa, A.C.F.M.

2014-01-01

In this work it was used magnetic nanoparticles Ni_0_,_2Cu_0_,_3Zn_0_,_5Fe_2O_4, chemical and thermally stable, under different conditions in catalysis for biodiesel. The magnetic characteristic of such material allows the catalyst recovery after the reactions by applying a permanent magnet. It was proposed to evaluate the performance of the nanomagnetic catalyst Ni_0_,_2Cu_0_,_3Zn_0_,_5Fe_2O_4 in the transesterification, modifying the processing variables (temperature, time, molar ratio of oil:alcohol and catalyst amount). The nanoparticles were synthesized by combustion reaction and characterized by XRD, TG, BET, magnetic measurements and gas chromatography. The results revealed the formation of inverse spinel phase, type B(AB)_2O_4, presenting isotherm profile classified as type V, with hysteresis loop of type 3 (H3). The magnetic hysteresis curve showed a characteristic behavior of soft magnetic material. GC analysis confirmed that nanoparticles were catalytically active, since they were superior to the reaction conducted without the catalyst presence. Besides, the reactions suffered considerable influence due to the changes of the independent variables. (author)

Coupling chemical and biological catalysis: a flexible paradigm for producing biobased chemicals.

Science.gov (United States)

Schwartz, Thomas J; Shanks, Brent H; Dumesic, James A

2016-04-01

Advances in metabolic engineering have allowed for the development of new biological catalysts capable of selectively de-functionalizing biomass to yield platform molecules that can be upgraded to biobased chemicals using high efficiency continuous processing allowed by heterogeneous chemical catalysis. Coupling these disciplines overcomes the difficulties of selectively activating COH bonds by heterogeneous chemical catalysis and producing petroleum analogues by biological catalysis. We show that carboxylic acids, pyrones, and alcohols are highly flexible platforms that can be used to produce biobased chemicals by this approach. More generally, we suggest that molecules with three distinct functionalities may represent a practical upper limit on the extent of functionality present in the platform molecules that serve as the bridge between biological and chemical catalysis. Copyright © 2016 Elsevier Ltd. All rights reserved.

Evaluation of Biodiesel Production, Engine Performance, and Emissions

Science.gov (United States)

Gürü, Metin; Keskïn, Ali

2016-08-01

Nowadays, to decrease environmental pollution and dependence on fossil-based fuels, research on alternative renewable energy sources has been increasing. One such renewable energy source is biodiesel, which is used as an alternative fuel for diesel engines. Biodiesel is renewable, nontoxic, biodegradable, and environmentally friendly. Biodiesel is domestically produced from vegetable oil (edible or nonedible), animal fat, and used cooking oils. In the biodiesel production process, oil or fat undergoes transesterification reaction through use of simple alcohols such as methanol, ethanol, propanol, butanol, etc. Use of methanol is most feasible because of its low cost, and physical and chemical advantages. Acid catalysis, alkali catalysis, and enzyme catalysis are usually used to improve the reaction rate and yield. Glycerol is a byproduct of the reaction and can be used as an industrial raw material. In this study, biodiesel production methods (direct use, pyrolysis, microemulsion, transesterification, supercritical processes, ultrasound- assisted, and microwave-assisted) and types of catalyst (homogeneous, heterogeneous, and enzyme) have been evaluated and compared. In addition, the effects of biodiesel and its blends on diesel engine performance and exhaust emissions are described and reviewed.

Gold Redox Catalysis through Base-Initiated Diazonium Decomposition toward Alkene, Alkyne, and Allene Activation.

Science.gov (United States)

Dong, Boliang; Peng, Haihui; Motika, Stephen E; Shi, Xiaodong

2017-08-16

The discovery of photoassisted diazonium activation toward gold(I) oxidation greatly extended the scope of gold redox catalysis by avoiding the use of a strong oxidant. Some practical issues that limit the application of this new type of chemistry are the relative low efficiency (long reaction time and low conversion) and the strict reaction condition control that is necessary (degassing and inert reaction environment). Herein, an alternative photofree condition has been developed through Lewis base induced diazonium activation. With this method, an unreactive Au I catalyst was used in combination with Na 2 CO 3 and diazonium salts to produce a Au III intermediate. The efficient activation of various substrates, including alkyne, alkene and allene was achieved, followed by rapid Au III reductive elimination, which yielded the C-C coupling products with good to excellent yields. Relative to the previously reported photoactivation method, our approach offered greater efficiency and versatility through faster reaction rates and broader reaction scope. Challenging substrates such as electron rich/neutral allenes, which could not be activated under the photoinitiation conditions (<5 % yield), could be activated to subsequently yield the desired coupling products in good to excellent yield. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalysis in Molten Ionic Media

DEFF Research Database (Denmark)

Boghosian, Soghomon; Fehrmann, Rasmus

2013-01-01

This chapter deals with catalysis in molten salts and ionic liquids, which are introduced and reviewed briefly, while an in-depth review of the oxidation catalyst used for the manufacturing of sulfuric acid and cleaning of flue gas from electrical power plants is the main topic of the chapter...

LSENS: A General Chemical Kinetics and Sensitivity Analysis Code for homogeneous gas-phase reactions. Part 1: Theory and numerical solution procedures

Science.gov (United States)

Radhakrishnan, Krishnan

1994-01-01

LSENS, the Lewis General Chemical Kinetics and Sensitivity Analysis Code, has been developed for solving complex, homogeneous, gas-phase chemical kinetics problems and contains sensitivity analysis for a variety of problems, including nonisothermal situations. This report is part 1 of a series of three reference publications that describe LENS, provide a detailed guide to its usage, and present many example problems. Part 1 derives the governing equations and describes the numerical solution procedures for the types of problems that can be solved. The accuracy and efficiency of LSENS are examined by means of various test problems, and comparisons with other methods and codes are presented. LSENS is a flexible, convenient, accurate, and efficient solver for chemical reaction problems such as static system; steady, one-dimensional, inviscid flow; reaction behind incident shock wave, including boundary layer correction; and perfectly stirred (highly backmixed) reactor. In addition, the chemical equilibrium state can be computed for the following assigned states: temperature and pressure, enthalpy and pressure, temperature and volume, and internal energy and volume. For static problems the code computes the sensitivity coefficients of the dependent variables and their temporal derivatives with respect to the initial values of the dependent variables and/or the three rate coefficient parameters of the chemical reactions.

Modelling non-homogeneous stochastic reaction-diffusion systems: the case study of gemcitabine-treated non-small cell lung cancer growth.

Science.gov (United States)

Lecca, Paola; Morpurgo, Daniele

2012-01-01

Reaction-diffusion based models have been widely used in the literature for modeling the growth of solid tumors. Many of the current models treat both diffusion/consumption of nutrients and cell proliferation. The majority of these models use classical transport/mass conservation equations for describing the distribution of molecular species in tumor spheroids, and the Fick's law for describing the flux of uncharged molecules (i.e oxygen, glucose). Commonly, the equations for the cell movement and proliferation are first order differential equations describing the rate of change of the velocity of the cells with respect to the spatial coordinates as a function of the nutrient's gradient. Several modifications of these equations have been developed in the last decade to explicitly indicate that the tumor includes cells, interstitial fluids and extracellular matrix: these variants provided a model of tumor as a multiphase material with these as the different phases. Most of the current reaction-diffusion tumor models are deterministic and do not model the diffusion as a local state-dependent process in a non-homogeneous medium at the micro- and meso-scale of the intra- and inter-cellular processes, respectively. Furthermore, a stochastic reaction-diffusion model in which diffusive transport of the molecular species of nutrients and chemotherapy drugs as well as the interactions of the tumor cells with these species is a novel approach. The application of this approach to he scase of non-small cell lung cancer treated with gemcitabine is also novel. We present a stochastic reaction-diffusion model of non-small cell lung cancer growth in the specification formalism of the tool Redi, we recently developed for simulating reaction-diffusion systems. We also describe how a spatial gradient of nutrients and oncological drugs affects the tumor progression. Our model is based on a generalization of the Fick's first diffusion law that allows to model diffusive transport in non-homogeneous

Domino-Fluorination-Protodefluorination Enables Decarboxylative Cross-Coupling of α-Oxocarboxylic Acids with Styrene via Photoredox Catalysis.

Science.gov (United States)

Zhang, Muliang; Xi, Junwei; Ruzi, Rehanguli; Li, Nan; Wu, Zhongkai; Li, Weipeng; Zhu, Chengjian

2017-09-15

Domino-fluorination-protodefluorination decarboxylative cross-coupling of α-keto acids with styrene has been developed via photoredox catalysis. The critical part of this strategy is the formation of the carbon-fluorine (C-F) bond by the capture of a carbon-centered radical intermediate, which will overcome side reactions during the styrene radical functionalization process. Experimental studies have provided evidence indicating a domino-fluorination-protodefluorination pathway with α-keto acid initiating the photoredox cycle. The present catalytic protocol also affords a novel approach for the construction of α,β-unsaturated ketones under mild conditions.

2008 Gordon Research Conference on Catalysis [Conference summary report

Energy Technology Data Exchange (ETDEWEB)

Soled, Stuart L.; Gray, Nancy Ryan

2009-01-01

The GRC on Catalysis is one of the most prestigious catalysis conferences as it brings together leading researchers from around the world to discuss their latest, most exciting work in catalysis. The 2008 conference will continue this tradition. The conference will cover a variety of themes including new catalytic materials, theoretical and experimental approaches to improve understanding of kinetics and transport phenomena, and state of the art nanoscale characterization probes to monitor active sites. The conference promotes interactions among established researchers and young scientists. It provides a venue for students to meet, talk to and learn from some of the world leading researchers in the area. It also gives them a platform for displaying their own work during the poster sessions. The informal nature of the meeting, excellent quality of the presentations and posters, and ability to meet many outstanding colleagues makes this an excellent conference.

Studies of Metal-Metal Bonded Compounds in Catalysis

Energy Technology Data Exchange (ETDEWEB)

Berry, John F. [Univ. of Wisconsin, Madison, WI (United States)

2018-01-19

The overall goals of this research are (1) to define the fundamental coordination chemistry underlying successful catalytic transformations promoted by metal-metal bonded compounds, and (2) to explore new chemical transformations that occur at metal-metal bonded sites that could lead to the discovery of new catalytic processes. Transformations of interest include metal-promoted reactions of carbene, nitrene, or nitrido species to yield products with new C–C and C–N bonds, respectively. The most promising suite of transition metal catalysts for these transformations is the set of metal-metal bonded coordination compounds of Ru and Rh of the general formula M₂(ligand)₄, where M = Ru or Rh and ligand = a monoanionic, bridging ligand such as acetate. Development of new catalysts and improvement of catalytic conditions have been stymied by a general lack of knowledge about the nature of highly reactive intermediates in these reactions, the knowledge that is to be supplied by this work. Our three specific objectives for this year have been (A) to trap, isolate, and characterize new reactive intermediates of general relevance to catalysis, (B) to explore the electronic structure and reactivity of these unusual species, and how these two properties are interrelated, and (C) to use our obtained mechanistic knowledge to design new catalysts with a focus on Earth-abundant first-row transition metal compounds.

Cluster size matters: Size-driven performance of subnanometer clusters in catalysis, electrocatalysis and Li-air batteries

Science.gov (United States)

Vajda, Stefan

2015-03-01

This paper discusses the strongly size-dependent performance of subnanometer cluster based catalysts in 1) heterogeneous catalysis, 2) electrocatalysis and 3) Li-air batteries. The experimental studies are based on I. fabrication of ultrasmall clusters with atomic precision control of particle size and their deposition on oxide and carbon based supports; II. test of performance, III. in situand ex situ X-ray characterization of cluster size, shape and oxidation state; and IV.electron microscopies. Heterogeneous catalysis. The pronounced effect of cluster size and support on the performance of the catalyst (catalyst activity and the yield of Cn products) will be illustrated on the example of nickel and cobalt clusters in Fischer-Tropsch reaction. Electrocatalysis. The study of the oxygen evolution reaction (OER) on size-selected palladium clusters supported on ultrananocrystalline diamond show pronounced size effects. While Pd4 clusters show no reaction, Pd6 and Pd17 clusters are among the most active catalysts known (in in terms of turnover rate per Pd atom). The system (soft-landed Pd4, Pd6, or Pd17 clusters on an UNCD Si coated electrode) shows stable electrochemical potentials over several cycles, and the characterization of the electrodes show no evidence for evolution or dissolution of either the support Theoretical calculations suggest that this striking difference may be a demonstration that bridging Pd-Pd sites, which are only present in three-dimensional clusters, are active for the oxygen evolution reaction in Pd6O6. Li-air batteries. The studies show that sub-nm silver clusters have dramatic size-dependent effect on the lowering of the overpotential, charge capacity, morphology of the discharge products, as well as on the morphology of the nm size building blocks of the discharge products. The results suggest that by precise control of the active surface sites on the cathode, the performance of Li-air cells can be significantly improved

Process for forming a homogeneous oxide solid phase of catalytically active material

Science.gov (United States)

Perry, Dale L.; Russo, Richard E.; Mao, Xianglei

1995-01-01

A process is disclosed for forming a homogeneous oxide solid phase reaction product of catalytically active material comprising one or more alkali metals, one or more alkaline earth metals, and one or more Group VIII transition metals. The process comprises reacting together one or more alkali metal oxides and/or salts, one or more alkaline earth metal oxides and/or salts, one or more Group VIII transition metal oxides and/or salts, capable of forming a catalytically active reaction product, in the optional presence of an additional source of oxygen, using a laser beam to ablate from a target such metal compound reactants in the form of a vapor in a deposition chamber, resulting in the deposition, on a heated substrate in the chamber, of the desired oxide phase reaction product. The resulting product may be formed in variable, but reproducible, stoichiometric ratios. The homogeneous oxide solid phase product is useful as a catalyst, and can be produced in many physical forms, including thin films, particulate forms, coatings on catalyst support structures, and coatings on structures used in reaction apparatus in which the reaction product of the invention will serve as a catalyst.

Industrial applications of plasma, microwave and ultrasound techniques : nitrogen-fixation and hydrogenation reactions

NARCIS (Netherlands)

Hessel, V.; Cravotto, G.; Fitzpatrick, P.; Patil, B.S.; Lang, J.; Bonrath, W.

2013-01-01

The MAPSYN project (Microwave, Acoustic and Plasma assisted SYNtheses) aims at nitrogen-fixation reactions intensified by plasma catalysis and selective hydrogenations intensified by microwaves, possibly assisted by ultrasound. Energy efficiency is the key motif of the project and the call of the

Experimental and theoretical investigation of Fe-catalysis phenomenon in hydrogen thermal desorption form hydrocarbon plasma-discharge films from T-10 tokamak

International Nuclear Information System (INIS)

Stankevich, V.G.; Svechnikov, N.Y.; Lebedev, A.M.; Menshikov, K.A.; Kolbasov, B.N.; Sukhanov, L.P.

2017-01-01

A comprehensive study of hydrocarbon films obtained in the plasma discharge of large fusion facilities will allow the minimization of parasitic capture. The investigation of the effect of Fe impurities on D 2 thermal desorption (TD) from homogeneous CD x films (x ∼ 0.5) formed in the D-plasma discharge of the T-10 tokamak were carried out. The experimental TD spectra of the films showed 2 groups of peaks at 650-850 K and 900-1000 K for 2 adsorption states. The main result of the iron catalysis effect consists in the shift of the high-temperature peak by -24 K and in the increase in the fraction of the weakly bonded adsorption states. To describe the effect of iron impurities on TD of hydrogen isotopes, a structural cluster model based on the interaction of the Fe + ion with the 1,3-C 6 H 8 molecule was proposed. The potential energy surfaces of chemical reactions with the H 2 elimination were calculated using ab initio methods of quantum chemistry. It was established that the activation barrier of hydrogen TD is reduced by about 1 eV due to the interaction of the Fe + ion with the π-subsystem of the 1,3-C 6 H 8 molecule leading to a redistribution of the double bonds along the carbon system

Experimental and theoretical investigation of Fe-catalysis phenomenon in hydrogen thermal desorption from hydrocarbon plasma-discharge films from T-10 tokama

Science.gov (United States)

Stankevich, Vladimir G.; Sukhanov, Leonid P.; Svechnikov, Nicolay Yu.; Lebedev, Alexey M.; Menshikov, Kostantin A.; Kolbasov, Boris N.

2017-10-01

Investigations of the effect of Fe impurities on D2 thermal desorption (TD) from homogeneous CDx films (x ˜ 0.5) formed in the D-plasma discharge of the T-10 tokamak were carried out. The experimental TD spectra of the films showed two groups of peaks at 650-850 K and 900-1000 K for two adsorption states. The main result of the iron catalysis effect consists in the shift of the high-temperature peak by -24 K and in the increase in the fraction of the weakly bonded adsorption states. To describe the effect of iron impurities on TD of hydrogen isotopes, a structural cluster model based on the interaction of the Fe+ ion with the 1,3-C6H8 molecule was proposed. The potential energy surfaces of chemical reactions with the H2 elimination were calculated using ab initio methods of quantum chemistry. It was established that the activation barrier of hydrogen TD is reduced by about 1 eV due to the interaction of the Fe+ ion with the π-subsystem of the 1,3-C6H8 molecule leading to a redistribution of the double bonds along the carbon system. Contribution to the topical issue "Plasma Sources and Plasma Processes (PSPP)"", edited by Luis Lemos Alves, Thierry Belmonte and Tiberiu Minea

Asymmetric Aminalization via Cation-Binding Catalysis

DEFF Research Database (Denmark)

Park, Sang Yeon; Liu, Yidong; Oh, Joong Suk

2018-01-01

Asymmetric cation-binding catalysis, in principle, can generate "chiral" anionic nucleophiles, where the counter cations are coordinated within chiral environments. Nitrogen-nucleophiles are intrinsically basic, therefore, its use as nucleophiles is often challenging and limiting the scope of the...

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

Science.gov (United States)

Nguyen, Luan; Tao, Franklin Feng

2018-02-01

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

Microwave activation of palladium nanoparticles for enhanced ethanol electrocatalytic oxidation reaction in alkaline medium

CSIR Research Space (South Africa)

Rohwer, MB

2015-02-01

Full Text Available in alkaline medium (in terms of high mass activity stability and fast reaction kinetics). The remarkable microwave-induced properties on the Pd catalyst promise to revolutionize the use of microwave for catalyst activation for enhanced heterogeneous catalysis...

Purification, properties, and N-terminal amino acid sequence of homogeneous Escherichia coli 2-amino-3-ketobutyrate CoA ligase, a pyridoxal phosphate-dependent enzyme.

Science.gov (United States)

Mukherjee, J J; Dekker, E E

1987-10-25

Starting with 100 g (wet weight) of a mutant of Escherichia coli K-12 forced to grow on L-threonine as sole carbon source, we developed a 6-step procedure that provides 30-40 mg of homogeneous 2-amino-3-ketobutyrate CoA ligase (also called aminoacetone synthetase or synthase). This ligase, which catalyzes the cleavage/condensation reaction between 2-amino-3-ketobutyrate (the presumed product of the L-threonine dehydrogenase-catalyzed reaction) and glycine + acetyl-CoA, has an apparent molecular weight approximately equal to 85,000 and consists of two identical (or nearly identical) subunits with Mr = 42,000. Computer analysis of amino acid composition data, which gives the best fit nearest integer ratio for each residue, indicates a total of 387 amino acids/subunit with a calculated Mr = 42,093. Stepwise Edman degradation provided the N-terminal sequence of the first 21 amino acids. It is a pyridoxal phosphate-dependent enzyme since (a) several carbonyl reagents caused greater than 90% loss of activity, (b) dialysis against buffer containing hydroxylamine resulted in 89% loss of activity coincident with an 86% decrease in absorptivity at 428 nm, (c) incubation of the apoenzyme with 20 microM pyridoxal phosphate showed a parallel recovery (greater than 90%) of activity and 428-nm absorptivity, and (d) reduction of the holoenzyme with NaBH4 resulted in complete inactivation, disappearance of a new absorption maximum at 333 nm. Strict specificity for glycine is shown but acetyl-CoA (100%), n-propionyl-CoA (127%), or n-butyryl-CoA (16%) is utilized in the condensation reaction. Apparent Km values for acetyl-CoA, n-propionyl-CoA, and glycine are 59 microM, 80 microM, and 12 mM, respectively; the pH optimum = 7.5. Added divalent metal ions or sulfhydryl compounds inhibited catalysis of the condensation reaction.

Isoporphyrin Intermediate in Heme Oxygenase Catalysis

Science.gov (United States)

Evans, John P.; Niemevz, Fernando; Buldain, Graciela; de Montellano, Paul Ortiz

2008-01-01

Human heme oxygenase-1 (hHO-1) catalyzes the O2- and NADPH-dependent oxidation of heme to biliverdin, CO, and free iron. The first step involves regiospecific insertion of an oxygen atom at the α-meso carbon by a ferric hydroperoxide and is predicted to proceed via an isoporphyrin π-cation intermediate. Here we report spectroscopic detection of a transient intermediate during oxidation by hHO-1 of α-meso-phenylheme-IX, α-meso-(p-methylphenyl)-mesoheme-III, and α-meso-(p-trifluoromethylphenyl)-mesoheme-III. In agreement with previous experiments (Wang, J., Niemevz, F., Lad, L., Huang, L., Alvarez, D. E., Buldain, G., Poulos, T. L., and Ortiz de Montellano, P. R. (2004) J. Biol. Chem. 279, 42593–42604), only the α-biliverdin isomer is produced with concomitant formation of the corresponding benzoic acid. The transient intermediate observed in the NADPH-P450 reductase-catalyzed reaction accumulated when the reaction was supported by H2O2 and exhibited the absorption maxima at 435 and 930 nm characteristic of an isoporphyrin. Product analysis by reversed phase high performance liquid chromatography and liquid chromatography electrospray ionization mass spectrometry of the product generated with H2O2 identified it as an isoporphyrin that, on quenching, decayed to benzoylbiliverdin. In the presence of H218O2, one labeled oxygen atom was incorporated into these products. The hHO-1-isoporphyrin complexes were found to have half-lives of 1.7 and 2.4 h for the p-trifluoromethyl- and p-methyl-substituted phenylhemes, respectively. The addition of NADPH-P450 reductase to the H2O2-generated hHO-1-isoporphyrin complex produced α-biliverdin, confirming its role as a reaction intermediate. Identification of an isoporphyrin intermediate in the catalytic sequence of hHO-1, the first such intermediate observed in hemoprotein catalysis, completes our understanding of the critical first step of heme oxidation. PMID:18487208

Tandem rhodium catalysis: exploiting sulfoxides for asymmetric transition-metal catalysis.

Science.gov (United States)

Kou, K G M; Dong, V M

2015-06-07

Sulfoxides are uncommon substrates for transition-metal catalysis due to their propensity to inhibit catalyst turnover. In a collaborative effort with Ken Houk, we developed the first dynamic kinetic resolution (DKR) of allylic sulfoxides using asymmetric rhodium-catalyzed hydrogenation. A detailed mechanistic analysis of this transformation using both experimental and theoretical methods revealed rhodium to be a tandem catalyst that promoted both hydrogenation of the alkene and racemization of the allylic sulfoxide. Using a combination of deuterium labelling and DFT studies, a novel mode of allylic sulfoxide racemization via a Rh(III)-π-allyl intermediate was identified.

Stereodivergent Mannich reaction of bis(trimethylsilyl)ketene acetals with N-tert-butanesulfinyl imines by Lewis acid or Lewis base activation, a one-pot protocol to obtain chiral β-amino acids.

Science.gov (United States)

Cantú-Reyes, Margarita; Alvarado-Beltrán, Isabel; Ballinas-Indilí, Ricardo; Álvarez-Toledano, Cecilio; Hernández-Rodríguez, Marcos

2017-09-20

We report a one-pot synthesis of chiral β 2,2,3 -amino acids by the Mannich addition of bistrimethylsilyl ketene acetals to N-tert-butanesulfinyl imines followed by the removal of the chiral auxiliary. The synthesis and isolation of pure β-amino acid hydrochlorides were conducted under mild conditions, without strong bases and this method is operationally simple. The stereoselective reaction was promoted by two different activation methods that lead to different stereoisomers: (1) Lewis Acid (LA) catalysis with boron trifluoride diethyl etherate and (2) Lewis Base (LB) catalysis with tetrabutylammonium difluorotriphenylsilicate. The reaction presented good diastereoselectivity with LB activation and moderate to good dr with LA catalysis. The exceptions in both protocols were imines with electron donating groups in the aromatic ring.

Improving Pullulanase Catalysis via Reversible Immobilization on Modified Fe3O4@Polydopamine Nanoparticles.

Science.gov (United States)

Wang, Jianfeng; Liu, Zhongmei; Zhou, Zhemin

2017-08-01

To improve the catalysis of pullulanase from Anoxybacillus sp.WB42, Fe 3 O 4 @polydopamine nanoparticles (Fe 3 O 4 @PDA) were prepared and modified with functional groups for immobilization of pullulanases via covalent binding or ionic adsorption. Immobilized pullulanases had lower thermal stability than that of free pullulanase, whereas their catalysis depended on the surface characteristics of nanoparticles. As for covalent immobilization of pullulanases onto Fe 3 O 4 @PDA derivatives, the spacer grafted onto Fe 3 O 4 @PDA made the catalytic efficiency of pullulanase increase up to the equivalence of free enzyme but dramatically reduced the pullulanase thermostability. In contrast, pullulanases bounded ionically to Fe 3 O 4 @PDA derivatives had higher activity recovery and catalytic efficiency, and their catalytic behaviors varied with the modifier grafted onto Fe 3 O 4 @PDA. Among these immobilized pullulanases, ionic adsorption of pullulanase on Fe 3 O 4 @PDA-polyethyleneimine-glycidyltrimethylammonium gave a high-performance and durable catalyst, which displayed not only 1.5-fold increase in catalytic efficiency compared to free enzyme but also a significant improvement in operation stability with a half of initial activity after 27 consecutive cycles with a total reaction time of 13.5 h, and was reversible, making this nanoparticle reusable for immobilization.

Heterogeneous catalysis in highly sensitive microreactors

DEFF Research Database (Denmark)

Olsen, Jakob Lind

This thesis present a highly sensitive silicon microreactor and examples of its use in studying catalysis. The experimental setup built for gas handling and temperature control for the microreactor is described. The implementation of LabVIEW interfacing for all the experimental parts makes...

Electrospun doping of carbon nanotubes and platinum nanoparticles into the β-phase polyvinylidene difluoride nanofibrous membrane for biosensor and catalysis applications.

Science.gov (United States)

Zhang, Panpan; Zhao, Xinne; Zhang, Xuan; Lai, Yue; Wang, Xinting; Li, Jingfeng; Wei, Gang; Su, Zhiqiang

2014-05-28

A novel β-phase polyvinylidene difluoride (PVDF) nanofibrous membrane decorated with multiwalled carbon nanotubes (MWCNTs) and platinum nanoparticles (PtNPs) was fabricated by an improved electrospinning technique. The morphology of the fabricated PVDF-MWCNT-PtNP nanofibrous membrane was observed by scanning electron microscopy, and the formation of high β-phase in the hybrid nanofibrous membrane was investigated by Fourier transform infrared spectroscopy and differential scanning calorimetry. The uniform dispersion of MWCNTs and PtNPs in the PVDF hybrid nanofibrous membrane and their interaction were explored by transmission electron microscopy and X-ray diffraction. For the first time, we utilized this created PVDF-MWCNT-PtNP nanofibrous membrane for biosensor and catalysis applications. The nonenzymatic amperometric biosensor with highly stable and sensitive, and selective detection of both H2O2 and glucose was successfully fabricated based on the electrospun PVDF-MWCNT-PtNP nanofibrous membrane. In addition, the catalysis of the hybrid nanofibrous membrane for oxygen reduction reaction was tested, and a good catalysis performance was found. We anticipate that the strategies utilized in this work will not only guide the further design of functional nanofiber-based biomaterials and biodevices but also extend the potential applications in energy storage, cytology, and tissue engineering.

Transformation of Sorbitol to Biofuels by Heterogeneous Catalysis: Chemical and Industrial Considerations

International Nuclear Information System (INIS)

Vilcocq, L.; Cabiac, A.; Guillon, E.; Especel, C.; Duprez, D.

2013-01-01

Decreasing oil supplies and increasing energy demand provide incentives to find alternative fuels. First, the valorisation of edible crops for ethanol and bio-diesel production led to first generation biofuels. Nowadays, research is focused on lignocellulosic biomass as a source of renewable carbon (second generation biofuels). Whereas the cellulosic ethanol production is in progress, a new way consisting of the transformation of ex-lignocellulose sugars and polyols towards light hydrocarbons by heterogeneous catalysis in aqueous phase has been recently described. This process is performed under mild conditions (T < 300 deg. C and P < 50 bar). It requires on one hand hydrogen formation by catalytic reforming of carbohydrates in aqueous phase and on the other hand, the dehydration/hydrogenation of polyols leading to alkanes by selective C-O bond cleavages. The challenge here is to conceive multifunctional catalytic systems that are stable, active and selective under the reaction conditions. The aim of this article is to present the involved reactions, the catalytic systems described in literature for that kind of transformation and examples of industrial applications. (authors)

The Applications of Morphology Controlled ZnO in Catalysis

Directory of Open Access Journals (Sweden)

Yuhai Sun

2016-11-01

Full Text Available Zinc oxide (ZnO, with the unique chemical and physical properties of high chemical stability, broad radiation absorption range, high electrochemical coupling coefficient, and high photo-stability, is an attractive multifunctional material which has promoted great interest in many fields. What is more, its properties can be tuned by controllable synthesized morphologies. Therefore, after the success of the abundant morphology controllable synthesis, both the morphology-dependent ZnO properties and their related applications have been extensively investigated. This review concentrates on the properties of morphology-dependent ZnO and their applications in catalysis, mainly involved reactions on green energy and environmental issues, such as CO2 hydrogenation to fuels, methanol steam reforming to generate H2, bio-diesel production, pollutant photo-degradation, etc. The impressive catalytic properties of ZnO are associated with morphology tuned specific microstructures, defects or abilities of electron transportation, etc. The main morphology-dependent promotion mechanisms are discussed and summarized.

Complex Reaction Environments and Competing Reaction Mechanisms in Zeolite Catalysis: Insights from Advanced Molecular Dynamics

NARCIS (Netherlands)

De Wispelaere, K.; Ensing, B.; Ghysels, A.; Meijer, E.J.; van Van Speybroeck, V.

2015-01-01

The methanol-to-olefin process is a showcase example of complex zeolite-catalyzed chemistry. At real operating conditions, many factors affect the reactivity, such as framework flexibility, adsorption of various guest molecules, and competitive reaction pathways. In this study, the strength of first

Studies of structure change of iron sulfates and its catalysis; Ryusantetsukei shokubai no kozo henka to sono shokubai sayo

Energy Technology Data Exchange (ETDEWEB)

Ogata, E.; Horie, K. [The University of Tokyo, Tokyo (Japan). Faculty of Engineering; Nishijima, A. [National Institute of Materials and Chemical Research, Tsukuba (Japan)

1996-10-28

Since a huge amount of coal containing inorganic ash is treated for the commercial hydroliquefaction process, cheap catalysts widely distributing on the earth with large reserves are desired rather than expensive catalysts. This paper describes the effects of addition of sulfur on the catalysis of iron sulfates during the hydroconversion of 1-methylnaphthalene (1-MN). Reactions of 1-MN were conducted at the same charging amount of iron in the reaction system. Sulfur was directly added in the reaction system using ferrous sulfate (FeSO4) as precursor. Consequently, it was found that FeSO4 provides lower but similar catalytic activity to the synthetic pyrite catalyst prepared through the complex processes with the precise control. Thus, it was revealed that high performance pyrrhotite (Fe(1-x)S) catalyst can be prepared for the hydrogenation of aromatic-rings by adding solid sulfur into the reaction system using commercial reagent, FeSO4 as a precursor of the catalyst. 9 figs.

The major/minor concept: dependence of the selectivity of homogeneously catalyzed reactions on reactivity ratio and concentration ratio of the intermediates.

Science.gov (United States)

Schmidt, Thomas; Dai, Zhenya; Drexler, Hans-Joachim; Hapke, Marko; Preetz, Angelika; Heller, Detlef

2008-07-07

The homogeneously catalyzed asymmetric hydrogenation of prochiral olefins with cationic Rh(I) complexes is one of the best-understood selection processes. For some of the catalyst/substrate complexes, experimental proof points out the validation of the major/minor principle; the concentration-deficient minor substrate complex, which has very high reactivity, yields the excess enantiomer. As exemplified by the reaction system of [Rh(dipamp)(MeOH)2]+/methyl (Z)-alpha-acetamidocinnamate (dipamp=1,2-bis((o-methoxyphenyl)phenylphosphino)ethane), all six of the characteristic reaction rate constants have been previously identified. Recently, it was found that the major substrate complex can also yield the major enantiomer (lock-and-key principle). The differential equation system that results from the reaction sequence can be solved numerically for different hydrogen partial pressures by including the known equilibrium constants. The result displays the concentration-time dependence of all species that exist in the catalytic cycle. On the basis of the known constants as well as further experimental evidence, this work focuses on the examination of all principal possibilities resulting from the reaction sequence and leading to different results for the stereochemical outcome. From the simulation, the following conclusions can be drawn: 1) When an intermediate has extreme reactivity, its stationary concentration can become so small that it can no longer be the source of product selectivity; 2) in principle, the major/minor and lock-and-key principles can coexist depending on the applied pressure; 3) thermodynamically determined intermediate ratios can be completely converted under reaction conditions for a selection process; and 4) the increase in enantioselectivity with increasing hydrogen partial pressure, a phenomenon that is experimentally proven but theoretically far from being well-understood, can be explained by applying both the lock-and-key as well as the major

Kinetics of heterogeneous catalytic reactions

CERN Document Server

Boudart, Michel

2014-01-01

This book is a critical account of the principles of the kinetics of heterogeneous catalytic reactions in the light of recent developments in surface science and catalysis science. Originally published in 1984. The Princeton Legacy Library uses the latest print-on-demand technology to again make available previously out-of-print books from the distinguished backlist of Princeton University Press. These paperback editions preserve the original texts of these important books while presenting them in durable paperback editions. The goal of the Princeton Legacy Library is to vastly increase acc

Kinetic modeling study of homogeneous ignition of dimethyl ether/hydrogen and dimethyl ether/methane

International Nuclear Information System (INIS)

Wang, Ying; Liu, Hong; Ke, Xichun; Shen, Zhenxing

2017-01-01

Highlights: • Kinetic effects on the homogeneous ignitions of DME/H_2 and DME/CH_4 were studied. • Ignition delays with different DME blending ratio were determined and analyzed. • Different DME ignition combustion trends are found for H_2 and CH_4 addition. • Key elementary reactions are identified at different DME ratios and temperatures. - Abstract: Homogeneous ignition combustion of different proportion DME/H_2 and DME/CH_4 blend fuels in the air is investigated through the numerical simulation with the detailed chemistry at the low and high temperatures in this paper. The emphasis is the assessment of the kinetic effects involved in the ignition combustion of DME/H_2 and DME/CH_4 dual-fuel. It is found that the homogeneous ignition process has a clear distinction at the different temperatures. At the low temperature (900 K), the ignition delay times of DME/H_2 blends and DME/CH_4 blends both show an increase with a decrease of the DME blending ratio; furthermore, it is observed that CH_4 addition is more effective than H_2 addition in terms of delaying the DME homogeneous ignition due to the stable molecular structure of CH_4. At the high temperature (1400 K), with the decrease of DME blending ratio, the ignition delay time of DME/CH_4 blends is still increased, whereas, the ignition delay time of DME/H_2 blends is shortened. Sensitivity analysis, reaction path analysis and main pollutant species calculation are carried out and key elementary reactions involved in homogeneous ignition of DME/H_2 and DME/CH_4 dual fuel are also identified in this paper.

Current trends of surface science and catalysis

CERN Document Server

Park, Jeong Young

2014-01-01

Including detail on applying surface science in renewable energy conversion, this book covers the latest results on model catalysts including single crystals, bridging "materials and pressure gaps", and hot electron flows in heterogeneous catalysis.

Role of noble metal nanoparticles in DNA base damage and catalysis: a radiation chemical investigation

International Nuclear Information System (INIS)

Sharma, Geeta K.

2011-01-01

In the emerging field of nanoscience and nanotechnology, tremendous focus has been made by researcher to explore the applications of nanomaterials for human welfare by converting the findings into technology. Some of the examples have been the use of nanoparticles in the field of opto-electronic, fuel cells, medicine and catalysis. These wide applications and significance lies in the fact that nanoparticles possess unique physical and chemical properties very different from their bulk precursors. Numerous methods for the synthesis of noble nanoparticles with tunable shape and size have been reported in literature. The goal of our group is to use different methods of synthesis of noble metal nanoparticles (Au, Ag, Pt and Pd) and test their protective/damaging role towards DNA base damage induced by ionizing radiation (Au and Ag) and to test the catalytic activity of nanoparticles (Pt and Pd) in certain known organic synthesis/electron transfer reactions. Using radiation chemical techniques such as pulse radiolysis and steady state radiolysis complemented by the product analysis using HPLC/LC-MS, a detailed mechanism for the formation of transient species, kinetics leading to the formation of stable end products is studied in the DNA base damage induced by ionizing radiation in presence and absence of Au and Ag nanoparticles. Unraveling the complex interaction between catalysts and reactants under operando conditions is a key step towards gaining fundamental insight in catalysis. The catalytic activity of Pt and Pd nanoparticles in electron transfer and Suzuki coupling reactions has been determined. Investigations are currently underway to gain insight into the interaction between catalysts and reactants using time resolved spectroscopic measurements. These studies will be detailed during the presentation. (author)

Serial crystallography captures enzyme catalysis in copper nitrite reductase at atomic resolution from one crystal

Directory of Open Access Journals (Sweden)

Sam Horrell

2016-07-01

Full Text Available Relating individual protein crystal structures to an enzyme mechanism remains a major and challenging goal for structural biology. Serial crystallography using multiple crystals has recently been reported in both synchrotron-radiation and X-ray free-electron laser experiments. In this work, serial crystallography was used to obtain multiple structures serially from one crystal (MSOX to study in crystallo enzyme catalysis. Rapid, shutterless X-ray detector technology on a synchrotron MX beamline was exploited to perform low-dose serial crystallography on a single copper nitrite reductase crystal, which survived long enough for 45 consecutive 100 K X-ray structures to be collected at 1.07–1.62 Å resolution, all sampled from the same crystal volume. This serial crystallography approach revealed the gradual conversion of the substrate bound at the catalytic type 2 Cu centre from nitrite to nitric oxide, following reduction of the type 1 Cu electron-transfer centre by X-ray-generated solvated electrons. Significant, well defined structural rearrangements in the active site are evident in the series as the enzyme moves through its catalytic cycle, namely nitrite reduction, which is a vital step in the global denitrification process. It is proposed that such a serial crystallography approach is widely applicable for studying any redox or electron-driven enzyme reactions from a single protein crystal. It can provide a `catalytic reaction movie' highlighting the structural changes that occur during enzyme catalysis. The anticipated developments in the automation of data analysis and modelling are likely to allow seamless and near-real-time analysis of such data on-site at some of the powerful synchrotron crystallographic beamlines.

XXI symposium Modern chemical physics. Tuapse 2009. Summaries of reports

International Nuclear Information System (INIS)

2009-01-01

The materials of the XXI symposium Modern chemical physics, Tuapse 2009 (25 September - 6 October, 2009) are presented. Scientific program includes lectures, presentations and poster sessions on photochemistry and radiation chemistry, elementary processes, homogeneous and heterogeneous catalysis. The problems of chemical reaction kinetics, quantum chemistry, chemical spectroscopy, macromolecular chemistry are discussed. Topics of chemical physics of surface, nanochemistry, nanophysics and nanotechnology are treated [ru

Understanding plasma catalysis through modelling and simulation—a review

International Nuclear Information System (INIS)

Neyts, E C; Bogaerts, A

2014-01-01

Plasma catalysis holds great promise for environmental applications, provided that the process viability can be maximized in terms of energy efficiency and product selectivity. This requires a fundamental understanding of the various processes taking place and especially the mutual interactions between plasma and catalyst. In this review, we therefore first examine the various effects of the plasma on the catalyst and of the catalyst on the plasma that have been described in the literature. Most of these studies are purely experimental. The urgently needed fundamental understanding of the mechanisms underpinning plasma catalysis, however, may also be obtained through modelling and simulation. Therefore, we also provide here an overview of the modelling efforts that have been developed already, on both the atomistic and the macroscale, and we identify the data that can be obtained with these models to illustrate how modelling and simulation may contribute to this field. Last but not least, we also identify future modelling opportunities to obtain a more complete understanding of the various underlying plasma catalytic effects, which is needed to provide a comprehensive picture of plasma catalysis. (paper)

Ceria powders by homogeneous precipitation technique

International Nuclear Information System (INIS)

Ramanathan, S.; Roy, S.K.

2003-01-01

Formation of precursors for ceria by two homogeneous precipitation reactions - (cerium chloride + urea at 95 degC - called reaction A and cerium chloride + hexamethylenetetramine at 85 degC - called reaction B) - has been studied. The variation of size of the colloidal particles formed and the zeta potential of the suspensions with progress of reactions exhibited similar trends for both the precipitation processes. Particle size increased from 100 to 300 nm with increasing temperature and extent of reaction. The zeta potential was found to decrease with increasing extent of precipitation in the pH range of 5 to 7. Filtration and drying led to agglomeration of the fine particles in case of the precursor from reaction B. The as-formed precursors were crystalline - a basic carbonate in case of reaction A and hydrous oxide in case of reaction B. It was found that nano-crystalline ceria powders (average crystallite size -10 nm) formed above 400 degC from both these precursors. The agglomerate size (D50) of the precursors and ceria powders formed after calcination at 600 degC varied from 0.7 to 3 μm. Increasing calcination temperature up to 800 degC, increased the crystallite size (50 nm). The zeta potential variation with pH and concentration of an anionic dispersant (Calgon) for the ceria powders formed was studied to determine the ideal conditions for suspension stability. It was found to be maximum (i.e., the suspensions stable) in the pH range of 3 to 4 or Calgon concentration of 0.01 to 0.1 weight percent. (author)

Mechanistic and kinetic aspects of pentose dehydration towards furfural in aqueous media employing homogeneous catalysis

NARCIS (Netherlands)

Danon, B.; Marcotullio, G.; De Jong, W.

2013-01-01

In this paper both the mechanistic and kinetic aspects of furfural formation from pentoses in aqueous acidic media have been reviewed. Based on the reviewed literature, a comprehensive reaction mechanism has been proposed consisting of more than one route, all starting from acyclic xylose, and

The relationship between continuum homogeneity and statistical homogeneity in cosmology

International Nuclear Information System (INIS)

Stoeger, W.R.; Ellis, G.F.R.; Hellaby, C.

1987-01-01

Although the standard Friedmann-Lemaitre-Robertson-Walker (FLRW) Universe models are based on the concept that the Universe is spatially homogeneous, up to the present time no definition of this concept has been proposed that could in principle be tested by observation. Such a definition is here proposed, based on a simple spatial averaging procedure, which relates observable properties of the Universe to the continuum homogeneity idea that underlies the FLRW models. It turns out that the statistical homogeneity often used to describe the distribution of matter on a large scale does not imply spatial homogeneity according to this definition, and so cannot be simply related to a FLRW Universe model. Values are proposed for the homogeneity parameter and length scale of homogeneity of the Universe. (author)

Cooperative Effects Between Arginine and Glutamic Acid in the Amino Acid-Catalyzed Aldol Reaction.

Science.gov (United States)

Valero, Guillem; Moyano, Albert

2016-08-01

Catalysis of the aldol reaction between cyclohexanone and 4-nitrobenzaldehyde by mixtures of L-Arg and of L-Glu in wet dimethyl sulfoxide (DMSO) takes place with higher enantioselectivity (up to a 7-fold enhancement in the anti-aldol for the 1:1 mixture) than that observed when either L-Glu or L-Arg alone are used as the catalysts. These results can be explained by the formation of a catalytically active hydrogen-bonded complex between both amino acids, and demonstrate the possibility of positive cooperative effects in catalysis by two different α-amino acids. Chirality 28:599-605, 2016. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Kokes Awards for the 25th North American Catalysis Society Meeting

Energy Technology Data Exchange (ETDEWEB)

Pylypenko, Svitlana [Colorado School of Mines, Golden, CO (United States). Chemistry Dept. and Materials Science Program

2018-03-13

The biennial North American Catalysis Society (NACS) meeting is the premiere conferences in the area of catalysis, surface science, and reaction engineering. The 25th installment of this meeting will be held the week of June 4-9, 2017 in Denver, CO at the Hyatt Regency Hotel. Meeting objectives include bringing together leading researchers for intensive scientific exchange, providing students with an opportunity to present their work and interact with leaders in the field, and participate in service to scientific/technical community. Financial support to offset a portion of the associated costs – and specifically, registration fees, airline tickets, and hotel accommodations – encourages greater participation by graduate and undergraduate students, and often provides them the only opportunity to attend and meaningfully contribute to the conference. The funds sought in this proposal will be in support of the Richard J. Kokes Travel Award program. The eligibility criteria for undergraduates and graduate students applying for a merit-based Awards are that they must study at a university within the United States and present either a poster or presentation at the meeting. In the previous meeting in Pittsburgh, NACS received 200 applications and funded 110 students. Similarly, during the meeting in Louisville, NACS received 225 applications and funded nearly half of them. The NACS has an on-going tradition of encouraging graduate students (and more recently, undergraduates as well) to participate in and serve at the national meetings Providing financial support is one of the most effective means of accomplishing this goal. Their attendance significantly broadens their scientific training beyond what can be accomplished in the classroom, and offers them an opportunity to improve their communication and presentation skills. As an attendee to the 25th NAM, students will participate by listening to presentations from leading researchers from the U.S. and abroad, and they

Stable silver nanoclusters electrochemically deposited on nitrogen-doped graphene as efficient electrocatalyst for oxygen reduction reaction

Science.gov (United States)

Jin, Shi; Chen, Man; Dong, Haifeng; He, Bingyu; Lu, Huiting; Su, Lei; Dai, Wenhao; Zhang, Qiaochu; Zhang, Xueji

2015-01-01

Metal nanoclusters exhibit unusually high catalytic activity toward oxygen reduction reaction (ORR) due to their small size and unique electronic structures. However, controllable synthesis of stable metal nanoclusters is a challenge, and the durability of metal clusters suffers from the deficiency of dissolution, aggregation, and sintering during catalysis reactions. Herein, silver nanoclusters (AgNCs) (diameter , which is vital in high performance fuel cells, batteries and nanodevices.

Heterogeneous Metal Catalysts for Oxidation Reactions

Directory of Open Access Journals (Sweden)

Md. Eaqub Ali

2014-01-01

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

A thermo-diffusion system with Smoluchowski interactions : well-posedness and homogenization

NARCIS (Netherlands)

Krehel, O.; Aiki, T.; Muntean, A.

2014-01-01

We study the solvability and homogenization of a thermal-diffusion reaction problem posed in a periodically perforated domain. The system describes the motion of populations of hot colloidal particles interacting together via Smoluchowski production terms. The upscaled system, obtained via two-scale

Mechanical Homogenization Increases Bacterial Homogeneity in Sputum

Science.gov (United States)

Stokell, Joshua R.; Khan, Ammad

2014-01-01

Sputum obtained from patients with cystic fibrosis (CF) is highly viscous and often heterogeneous in bacterial distribution. Adding dithiothreitol (DTT) is the standard method for liquefaction prior to processing sputum for molecular detection assays. To determine if DTT treatment homogenizes the bacterial distribution within sputum, we measured the difference in mean total bacterial abundance and abundance of Burkholderia multivorans between aliquots of DTT-treated sputum samples with and without a mechanical homogenization (MH) step using a high-speed dispersing element. Additionally, we measured the effect of MH on bacterial abundance. We found a significant difference between the mean bacterial abundances in aliquots that were subjected to only DTT treatment and those of the aliquots which included an MH step (all bacteria, P = 0.04; B. multivorans, P = 0.05). There was no significant effect of MH on bacterial abundance in sputum. Although our results are from a single CF patient, they indicate that mechanical homogenization increases the homogeneity of bacteria in sputum. PMID:24759710

Microwaves in chemistry: Another way of heating reaction mixtures

Science.gov (United States)

Berlan, J.

1995-04-01

The question of a possible "microwave activation" of chemical reaction is discussed. In fact two cases should be distinguished: homogeneous or heterogeneous reaction mixtures. In homogeneous mixtures there are no (or very low) rate enhancements compared to a conventional heating, but some influence on chemioselectivity has been observed. These effects derive from fast and mass heating of microwaves, and probably, especially under reflux, from different boiling rates and/or overheating. With heterogeneous mixtures non conventional effects probably derive from mass heating and selective overheating. This is illustrated with several reactions: Diels-Alder, naphthalene sulphonation, preparation of cyanuric acid, hydrolysis of nitriles, transposition reaction on solid support.

CH4/air homogeneous autoignition: A comparison of two chemical kinetics mechanisms

KAUST Repository

Tingas, Efstathios Al.; Manias, Dimitris M.; Sarathy, Mani; Goussis, Dimitris A.

2018-01-01

Reactions contributing to the generation of the explosive time scale that characterise autoignition of homogeneous stoichiometric CH4/air mixture are identified using two different chemical kinetics models; the well known GRI-3.0 mechanism (53

Biosourced Polymetallic Catalysis: A Surprising and Efficient Means to Promote the Knoevenagel Condensation

Directory of Open Access Journals (Sweden)

Pierre-Alexandre Deyris

2018-03-01

Full Text Available Zn hyperaccumulator (Arabidobsis halleri and Zn accumulator Salix “Tordis” (Salix schwerinii × Salix viminalis have shown their interest in the phytoextraction of polluted brownfields. Herein, we explore a novel methodology based on the chemical valorization of Zn-rich biomass produced by these metallophyte plants. The approach is based on the use of polymetallic salts derived from plants as bio-based catalysts in organic chemistry. The formed ecocatalysts were characterized via ICP-MS, X-ray diffraction (XRD, Fourier transform infrared spectroscopy (FT-IR in order to precise the chemical composition, structure, and behavior of the formed materials. The Doebner-Knoevenagel reaction was chosen as model reaction to study their synthetic potential. Significant differences to usual catalysts such as zinc (II chloride are observed. They can principally be related to a mixture of unusual mineral species. DFT calculations were carried out on these salts in the context of the Gutmann theory. They allow the rationalization of experimental results. Finally, these new bio-based polymetallic catalysts illustrated the interest of this concept for green and sustainable catalysis.

Biosourced polymetallic catalysis: A surprising and efficient means to promote the Knoevenagel condensation

Science.gov (United States)

Deyris, Pierre-Alexandre; Bert, Valérie; Diliberto, Sébastien; Boulanger, Clotilde; Petit, Eddy; Legrand, Yves-Marie; Grison, Claude

2018-03-01

Zn hyperaccumulator (Arabidobsis halleri) and Zn accumulator Salix ‘Tordis’ (Salix schwerinii x S. viminalis) have shown their interest in the phytoextraction of polluted brownfields. Herein, we explore an innovative methodology based on the chemical valorization of Zn-rich biomass produced by these metallophyte plants. The approach is based on the direct use of polymetallic salts derived from plants as “Lewis acid” catalysts in organic chemistry. The formed ecocatalysts were characterized via ICP-MS, XRD, FT-IR in order to elucidate the chemical composition, structure and behavior of the formed materials. The Doebner-Knoevenagel reaction was chosen as model reaction to study their synthetic potential. Significant differences to conventional catalysts such as zinc (II) chloride are observed. They can principally be related to a mixture of unusual mineral species. DFT calculations were carried out on these salts in the context of the Gutmann theory. They allow the rationalization of experimental results. Finally, these new bio-based polymetallic catalysts illustrated the interest of this concept for green and sustainable catalysis.

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-10-01

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

Site selectivity of specific reaction steps important for catalysis

DEFF Research Database (Denmark)

Nielsen, Kenneth

) overlayer system. In the STM study of the structure sensitivity of the CO dissociation reaction on the Ru(0 1 54) sample, it was determined that after cooling the sample from 700K to 400K in 10-8Torr of CO or in the CO that was left after a TPD, the sample displayed periodic decorations on every other...... site, is the most stable conguration after dissociation. Preliminary results where the sample was exposed to high doses of CO, at a CO pressure of 10-5 Torr and a temperature of 550K (dissociation conditions) indicated that especially every other step had a very rough appearance after 7 min exposure...

Effect of Solvents on the Product Distribution and Reaction Rate of a Buchwald-Hartwig Amination Reaction

DEFF Research Database (Denmark)

Christensen, H.; Kiil, Søren; Dam-Johansen, Kim

2006-01-01

The Buchwald-Hartwig amination reaction between p-bromotoluene and piperazine in the presence of the homogeneous catalytic system Pd(dba)(2)/(+/-)-BINAP and the base NaO-t-Bu was investigated in two different classes of solvents: aprotic, nonpolar and aprotic, polar. The reaction was carried out...... solvent for the Buchwald-Hartwig amination reaction under the conditions applied was m-xylene....

On the origin of the cobalt particle size effects in Fischer−Tropsch catalysis

NARCIS (Netherlands)

den Breejen, J.P.|info:eu-repo/dai/nl/304837318; Radstake, P.B.|info:eu-repo/dai/nl/304829587; Bezemer, G.L.; Bitter, J.H.|info:eu-repo/dai/nl/160581435; Froseth, V.; Holmen, A.; de Jong, K.P.|info:eu-repo/dai/nl/06885580X

2009-01-01

The effects of metal particle size in catalysis are of prime scientific and industrial importance and call for a better understanding. In this paper the origin of the cobalt particle size effects in Fischer−Tropsch (FT) catalysis was studied. Steady-State Isotopic Transient Kinetic Analysis (SSITKA)

Metallic nanosystems in catalysis

International Nuclear Information System (INIS)

Bukhtiyarov, Valerii I; Slin'ko, Mikhail G

2001-01-01

The reactivities of metallic nanosystems in catalytic processes are considered. The activities of nanoparticles in catalysis are due to their unique microstructures, electronic properties and high specific surfaces of the active centres. The problems of increasing the selectivities of catalytic processes are discussed using several nanosystems as examples. The mutual effects of components of bimetallic nanoparticles are discussed. The prospects for theoretical and experimental investigations into catalytic nanosystems and the construction of industrial catalysts based on them are evaluated. The bibliography includes 207 references.

Functionalization of multi-walled carbon nanotubes with iron phthalocyanine via a liquid chemical reaction for oxygen reduction in alkaline media

Science.gov (United States)

Yan, Xiaomei; Xu, Xiao; Liu, Qin; Guo, Jia; Kang, Longtian; Yao, Jiannian

2018-06-01

Iron single-atom catalyst in form of iron-nitrogen-carbon structure possesses the excellent catalytic activity in various chemical reactions. However, exploring a sustainable and stable single-atom metal catalyst still faces a great challenge due to low yield and complicated synthesis. Here, we report a functional multi-wall carbon nanotubes modified with iron phthalocyanine molecules via a liquid chemical reaction and realize the performance of similar single-atom catalysis for oxygen reduction reaction. A serial of characterizations strongly imply the structure change of iron phthalocyanine molecule and its close recombination with multi-wall carbon nanotubes, which are in favor of ORR catalysis. Compared to commercial platinum-carbon catalyst, composites exhibit superior activity for oxygen reduction reaction with higher half-wave potential (0.86 V), lower Tafel slope (38 mV dec-1), higher limiting current density and excellent electrochemical stability. The corresponding Zinc-air battery also presents higher maximum power density and discharge stability. Therefore, these findings provide a facile route to synthesize a highly efficient non-precious metal carbon-based catalyst.

DNA-based asymmetric organometallic catalysis in water

NARCIS (Netherlands)

Oelerich, Jens; Roelfes, Gerard

2013-01-01

Here, the first examples of DNA-based organometallic catalysis in water that give rise to high enantioselectivities are described. Copper complexes of strongly intercalating ligands were found to enable the asymmetric intramolecular cyclopropanation of alpha-diazo-beta-keto sulfones in water. Up to

KCC1: First Nanoparticle developed by KAUST Catalysis Center

KAUST Repository

Basset, Jean-Marie

2010-08-01

KCC1 is the first Nanoparticle developed by KAUST Catalysis Center. Director of KAUST Catalysis Center, Dr. Jean-Marie Basset, Senior Research Scientist at KCC, Dr. Vivek Polshettiwar, and Dr. Dongkyu Cha of the Advanced Nanofabrication Imaging & Characterization Core Laboratory discuss the details of this recent discovery. This video was produced by KAUST Visualization Laboratory and KAUST Technology Transfer and Innovation - Terence McElwee, Director, Technology Transfer and Innovation - IP@kaust.edu.sa This technology is part of KAUST\\'s technology commercialization program that seeks to stimulate development and commercial use of KAUST-developed technologies. For more information email us at ip@kaust.edu.sa.

Comparison of cell homogenization methods considering interaction effect between fuel cells and control rod cells

International Nuclear Information System (INIS)

Takeda, T.; Uto, N.

1988-01-01

Several methods to determine cell-averaged group cross sections and anisotropic diffusion coefficients which consider the interaction effect between core fuel cells and control rods or control rod followers have been compared to discuss the physical meaning included in cell homogenization. As the cell homogenization methods considered are the commonly used flux-weighting method, the reaction rate preservation method and the reactivity preservation method. These homogenization methods have been applied to control rod worth calculations in 1-D slab cores to investigate their applicability. (author). 6 refs, 2 figs, 9 tabs

Symmetry and asymmetry in mandelate racemase catalysis

International Nuclear Information System (INIS)

Whitman, C.P.; Hegeman, G.D.; Cleland, W.W.; Kenyon, G.L.

1985-01-01

Kinetic properties of mandelate racemase catalysis (Vmax, Km, deuterium isotope effects, and pH profiles) were all measured in both directions by the circular dichroic assay of Sharp. These results, along with those of studying interactions of mandelate racemase with resolved, enantiomeric competitive inhibitors [(R)- and (S)-alpha-phenylglycerates], indicate a high degree of symmetry in both binding and catalysis. Racemization of either enantiomer of mandelate in D 2 O did not show an overshoot region of molecular ellipticity in circular dichroic measurements upon approach to equilibrium. Both the absence of such an overshoot region and the high degree of kinetic symmetry are consistent with a one-base acceptor mechanism for mandelate racemase. On the other hand, results of irreversible inhibition with partially resolved, enantiomeric affinity labels [(R)- and (S)-alpha-phenylglycidates] reveal a ''functional asymmetry'' at the active site. Mechanistic proposals, consistent with these results, are presented

Iron(III Fluorinated Porphyrins: Greener Chemistry from Synthesis to Oxidative Catalysis Reactions

Directory of Open Access Journals (Sweden)

Susana L. H. Rebelo

2016-04-01

Full Text Available Iron(III fluorinated porphyrins play a central role in the biomimetics of heme enzymes and enable cleaner routes to the oxidation of organic compounds. The present work reports significant improvements in the eco-compatibility of the synthesis of 5,10,15,20-tetrakis-pentafluorophenylporphyrin (H2TPFPP and the corresponding iron complex [Fe(TPFPPCl], and the use of [Fe(TPFPPCl] as an oxidation catalyst in green conditions. The preparations of H2TPFPP and [Fe(TPFPPCl] typically use toxic solvents and can be made significantly greener and simpler using microwave heating and optimization of the reaction conditions. In the optimized procedure it was possible to eliminate nitrobenzene from the porphyrin synthesis and replace DMF by acetonitrile in the metalation reaction, concomitant with a significant reduction of reaction time and simplification of the purification procedure. The Fe(IIIporphyrin is then tested as catalyst in the selective oxidation of aromatics at room temperature using a green oxidant (hydrogen peroxide and green solvent (ethanol. Efficient epoxidation of indene and selective oxidation of 3,5-dimethylphenol and naphthalene to the corresponding quinones is observed.

Iron(III) Fluorinated Porphyrins: Greener Chemistry from Synthesis to Oxidative Catalysis Reactions.

Science.gov (United States)

Rebelo, Susana L H; Silva, André M N; Medforth, Craig J; Freire, Cristina

2016-04-12

Iron(III) fluorinated porphyrins play a central role in the biomimetics of heme enzymes and enable cleaner routes to the oxidation of organic compounds. The present work reports significant improvements in the eco-compatibility of the synthesis of 5,10,15,20-tetrakis-pentafluorophenylporphyrin (H₂TPFPP) and the corresponding iron complex [Fe(TPFPP)Cl], and the use of [Fe(TPFPP)Cl] as an oxidation catalyst in green conditions. The preparations of H₂TPFPP and [Fe(TPFPP)Cl] typically use toxic solvents and can be made significantly greener and simpler using microwave heating and optimization of the reaction conditions. In the optimized procedure it was possible to eliminate nitrobenzene from the porphyrin synthesis and replace DMF by acetonitrile in the metalation reaction, concomitant with a significant reduction of reaction time and simplification of the purification procedure. The Fe(III)porphyrin is then tested as catalyst in the selective oxidation of aromatics at room temperature using a green oxidant (hydrogen peroxide) and green solvent (ethanol). Efficient epoxidation of indene and selective oxidation of 3,5-dimethylphenol and naphthalene to the corresponding quinones is observed.

Toward whole-core neutron transport without spatial homogenization

International Nuclear Information System (INIS)

Lewis, E. E.

2009-01-01

, iteration between lattice and homogenized calculations yields two-dimensional whole-core results without homogenization error. In the third, planar lattice transport is synthesized with lower-order axial transport to obtain approximate three-dimensional results without planar homogenization. In all three, advances in the method of characteristics play a prominent role, and each rests on some form of equivalence intervention to preserve reaction rates and currents between lattice and homogenized calculations. The talk concludes with some conjectures concerning the potential of interface current, response matrix and related domain decomposition approaches as alternative paths toward achieving whole-core neutronics without homogenization. (author)

Radical copolymerization in homogenous medium and emulsion system monomers acrylonitrile/styrene

Directory of Open Access Journals (Sweden)

Boussehel H.

2013-09-01

Full Text Available This study examines the radical copolymerization in homogeneous and emulsion of the monomer system acrylonitrile/styrene. These copolymers are of great interest to the plastics industry, because they combine the good mechanical properties and implementation provided by the styrene units in the very high solvent resistance and extreme gas impermeability provided by the acrylonitrile units. The properties of a copolymer are directly related to its composition and distribution of monomer units in its macromolecular chains. Based on the reports of the couple reactivity's of monomers (AN/S found in the literature, the objective of the work is to provide theoretical simulation (by analytical and numerical integration of the equation of copolymerization: The kinetics of the reaction copolymerization of AN/S in a homogeneous medium and emulsion (drift composition, azeotropic and the microstructure (distribution of monomer sequences and the glass transition property of the macromolecular chains instant formed throughout the copolymerization reaction.

Liquid phase oxidation via heterogeneous catalysis organic synthesis and industrial applications

CERN Document Server

Clerici, Mario G

2013-01-01

Sets the stage for environmentally friendly industrial organic syntheses From basic principles to new and emerging industrial applications, this book offers comprehensive coverage of heterogeneous liquid-phase selective oxidation catalysis. It fully examines the synthesis, characterization, and application of catalytic materials for environmentally friendly organic syntheses. Readers will find coverage of all the important classes of catalysts, with an emphasis on their stability and reusability. Liquid Phase Oxidation via Heterogeneous Catalysis features contributions from an internation

Bio-inspired carbon electro-catalysis for the oxygen reduction reaction

OpenAIRE

Preuss, Kathrin; Kannuchamy, Vasanth Kumar; Marinovic, Adam; Isaacs, Mark; Wilson, Karen; Abrahams, Isaac; Titirici, Maria-Magdalena

2016-01-01

We report the synthesis, characterisation and catalytic performance of two nature-inspired biomass-derived electro-catalysts for the oxygen reduction reaction in fuel cells. The catalysts were prepared via pyrolysis of a real food waste (lobster shells) or by mimicking the composition of lobster shells using chitin and CaCO3 particles followed by acid washing. The simplified model of artificial lobster was prepared for better reproducibility. The calcium carbonate in both samples acts as a po...

Inertial effects in diffusion-limited reactions

International Nuclear Information System (INIS)

Dorsaz, N; Foffi, G; De Michele, C; Piazza, F

2010-01-01

Diffusion-limited reactions are commonly found in biochemical processes such as enzyme catalysis, colloid and protein aggregation and binding between different macromolecules in cells. Usually, such reactions are modeled within the Smoluchowski framework by considering purely diffusive boundary problems. However, inertial effects are not always negligible in real biological or physical media on typical observation time frames. This is all the more so for non-bulk phenomena involving physical boundaries, that introduce additional time and space constraints. In this paper, we present and test a novel numerical scheme, based on event-driven Brownian dynamics, that allows us to explore a wide range of velocity relaxation times, from the purely diffusive case to the underdamped regime. We show that our algorithm perfectly reproduces the solution of the Fokker-Planck problem with absorbing boundary conditions in all the regimes considered and is thus a good tool for studying diffusion-guided reactions in complex biological environments.

Micellar Catalysis of Diels-Alder Reactions : Substrate Positioning in the Micelle

NARCIS (Netherlands)

Rispens, Theo; Engberts, Jan B.F.N.

2002-01-01

We have studied the kinetics of the Diels-Alder reactions of cyclopentadiene, sorbyl alcohol, and sorbyltrimethylammonium bromide with a series of N-substituted maleimides in micellar media. Micellar rate constants have been determined and were found to be 20-40 times lower than the respective

Molecular Catalysis at Polarized Interfaces Created by Ferroelectric BaTiO3 (Postprint)

Science.gov (United States)

2017-02-06

densities of 20–120 mC cm2 are considerably larger than what is accessible in the parallel plate cell at voltages below the dielectric breakdown limit (at...attachment. The results of reactions performed with 4b are summarized in Fig. 5. When used as a homogeneous catalyst , 2 mM 4b reacted with 2mM 1 in CH2Cl2 to...exploited to control the selectivity of non-faradaic reactions. Polarized interfaces are commonly prepared by applying a voltage to an electrode in

Rapid trifluoromethylation and perfluoroalkylation of five-membered heterocycles by photoredox catalysis in continuous flow.

Science.gov (United States)

Straathof, Natan J W; Gemoets, Hannes P L; Wang, Xiao; Schouten, Jaap C; Hessel, Volker; Noël, Timothy

2014-06-01

Trifluoromethylated and perfluoroalkylated heterocycles are important building blocks for the synthesis of numerous pharmaceutical products, agrochemicals and are widely applied in material sciences. To date, trifluoromethylated and perfluoroalkylated hetero-aromatic systems can be prepared utilizing visible light photoredox catalysis methodologies in batch. While several limitations are associated with these batch protocols, the application of microflow technology could greatly enhance and intensify these reactions. A simple and straightforward photocatalytic trifluoromethylation and perfluoroalkylation method has been developed in continuous microflow, using commercially available photocatalysts and microflow components. A selection of five-membered hetero-aromatics were successfully trifluoromethylated (12 examples) and perfluoroalkylated (5 examples) within several minutes (8-20 min). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Environmental catalysis

Energy Technology Data Exchange (ETDEWEB)

Janssen, F.J.J.G.; Santen, R.A. van (eds.)

1999-04-01

Catalysts play key roles in the production of clean fuels, the conversion of waste and green raw materials into energy, clean combustion engines including control of NOx and soot production and reduction of greenhouse gases, production of clean water and polymers, as well as reduction from polymers to monometers. This book contains 15 chapters by experts in the field, on the theme of catalysts used to create a sustainable society. Chapters include: catalysts for renewable energy and chemicals, fuel cells, catalytic processes for high-quality transportation fuels; oxidative coupling of methane, methane utilisation via synthesis gas generation, catalytic combustion, catalytical removal of nitrate from water, contribution of catalysis towards the reduction of atmospheric air pollution (CO{sub 2}, CFCs, N{sub 2}O), ozone), emission control from mobile sources and from stationary sources, and deactivation, regeneration and recycling of hydroprocessing catalysts.

2010 CATALYSIS GORDON RESEARCH CONFERENCE, JUNE 27 - JULY 2, 2010, NEW LONDON, NEW HAMPSHIRE

Energy Technology Data Exchange (ETDEWEB)

Abhaya Datye

2010-07-02

Catalysis is a key technology for improving the quality of life while simultaneously reducing the adverse impact of human activities on the environment. The discovery of new catalytic processes and the improvement of existing ones are also critically important for securing the nation's energy supply. The GRC on Catalysis is considered one the most prestigious conference for catalysis research, bringing together leading researchers from both academia, industry and national labs to discuss the latest, most exciting research in catalysis and the future directions for the field. The 2010 GRC on Catalysis will follow time-honored traditions and feature invited talks from the world's leading experts in the fundamentals and applications of catalytic science and technology. We plan to have increased participation from industry. The extended discussions in the company of outstanding thinkers will stimulate and foster new science. The conference will include talks in the following areas: Alternative feedstocks for chemicals and fuels, Imaging and spectroscopy, Design of novel catalysts, Catalyst preparation fundamentals, Molecular insights through theory, Surface Science, Catalyst stability and dynamics. In 2010, the Catalysis conference will move to a larger conference room with a new poster session area that will allow 40 posters per session. The dorm rooms provide single and double accommodations, free WiFi and the registration fee includes all meals and the famous lobster dinner on Thursday night. Afternoons are open to enjoy the New England ambiance with opportunities for hiking, sailing, golf and tennis to create an outstanding conference that will help you network with colleagues, and make long lasting connections.

Value-added Chemicals from Biomass by Heterogeneous Catalysis

DEFF Research Database (Denmark)

Voss, Bodil

feedstock, having retained one C-C bond originating from the biomass precursor, the aspects of utilising heterogeneous catalysis for its conversion to value added chemicals is investigated. Through a simple analysis of known, but not industrialised catalytic routes, the direct conversion of ethanol....... The results of the thesis, taking one example of biomass conversion, show that the utilisation of biomass in the production of chemicals by heterogeneous catalysis is promising from a technical point of view. But risks of market price excursions dominated by fossil based chemicals further set a criterion...... been implemented. The subject on chemical production has received less attention. This thesis describes and evaluates the quest for an alternative conversion route, based on a biomass feedstock and employing a heterogeneous catalyst capable of converting the feedstock, to a value-added chemical...

Synthesis and Reactions of Five-Membered Heterocycles Using Phase Transfer Catalyst (PTC Techniques

Directory of Open Access Journals (Sweden)

Ahmed M. El-Sayed

2014-01-01

Full Text Available Phase transfer catalysts (PTCs have been widely used for the synthesis of organic compounds particularly in both liquid-liquid and solid-liquid heterogeneous reaction mixtures. They are known to accelerate reaction rates by facilitating formation of interphase transfer of species and making reactions between reagents in two immiscible phases possible. Application of PTC instead of traditional technologies for industrial processes of organic synthesis provides substantial benefits for the environment. On the basis of numerous reports it is evident that phase-transfer catalysis is the most efficient way for generation and reactions of many active intermediates. In this review we report various uses of PTC in syntheses and reactions of five-membered heterocycles compounds and their multifused rings.

Mass Transfer and Chemical Reaction Approach of the Kinetics of the Acetylation of Gadung Flour using Glacial Acetic Acid

Directory of Open Access Journals (Sweden)

Andri Cahyo Kumoro

2015-03-01

Full Text Available Acetylation is one of the common methods of modifying starch properties by introducing acetil (CH3CO groups to starch molecules at low temperatures. While most acetylation is conducted using starch as anhidroglucose source and acetic anhydride or vinyl acetate as nucleophilic agents, this work employ reactants, namely flour and glacial acetic acid. The purpose of this work are to study the effect of pH reaction and GAA/GF mass ratio on the rate of acetylation reaction and to determine its rate constants. The acetylation of gadung flour with glacial acetic acid in the presence of sodium hydroxide as a homogenous catalyst was studied at ambient temperature with pH ranging from 8-10 and different mass ratio of acetic acid : gadung flour (1:3; 1:4; and 1:5. It was found that increasing pH, lead to increase the degree of substitution, while increasing GAA/GF mass ratio caused such decreases in the degree of substitution, due to the hydrolysis of the acetylated starch. The desired starch acetylation reaction is accompanied by undesirable hydrolysis reaction of the acetylated starch after 40-50 minutes reaction time. Investigation of kinetics of the reaction observed that the value of mass transfer rate constant (Kcs is smaller than the surface reaction rate constant (k. Thus, it can be concluded that rate controlling step is mass transfer.  © 2015 BCREC UNDIP. All rights reservedReceived: 7th August 2014; Revised: 8th September 2014; Accepted: 14th September 2014How to Cite: Kumoro, A.C., Amelia, R. (2015. Mass Transfer and Chemical Reaction Approach of the Kinetics of the Acetylation of Gadung Flour using Glacial Acetic Acid. Bulletin of Chemical Reaction Engineering & Catalysis, 10 (1: 30-37. (doi:10.9767/bcrec.10.1.7181.30-37Permalink/DOI: http://dx.doi.org/10.9767/bcrec.10.1.7181.30-37

Heterogeneous catalysis contribution for the denitration of aqueous nuclear radioactive waste with formic acid

International Nuclear Information System (INIS)

Guenais, S.

2001-01-01

The chemical denitration aims to reduce the nitric acid concentration in nuclear fuel reprocessing aqueous wastes by adding formic acid as a reducing agent. The denitration reaction exhibits an induction period, which duration is related to the time needed by the key intermediate of the reaction, i.e. nitrous acid, to reach a threshold concentration in the reaction medium. The addition of a Pt/SiO 2 catalyst in the reaction mixture suppresses the induction period of the chemical denitration. The aim of the present work is to identify the role of Pt/SiO 2 in the catalytic denitration mechanism. The experimental work is based on the comparison of catalytic tests performed with various catalysts, in order to identify the intrinsic characteristics of Pt/SiO 2 that might influence its activity for the reaction. Catalytic denitration results show that Pt/SiO 2 acts only by speeding up the nitrous acid generation in the solution until its concentration reaches the threshold level of 0,01 mol L -1 in the experimental conditions. Catalysts activity is evaluated by quantifying the nitrous acid generated on the platinum surface during the induction period of the homogeneous denitration reaction. The large platinum aggregates reactivity is greater than the one of nano-sized particles. The study of the key step of the catalytic denitration reaction, the catalytic generation of nitrous acid, clarifies the role of Pt/SiO 2 . The homogeneous denitration is initiated thanks to a redox cycle on the catalyst surface: an initial oxidation of Pt 0 by nitric acid, which is reduced into nitrous acid, followed by the reduction of the passivated 'Pt ox ' by formic acid. Furthermore, a platinum reduction by formic acid prior to the catalytic test prevents any platinum leaching from the catalyst into the nitric solution, being all the more significant as platinum dispersion is high. (author)

Involvement of active oxygen in lipid peroxide radical reaction of epidermal homogenate following ultraviolet light exposure

International Nuclear Information System (INIS)

Nishi, J.; Ogura, R.; Sugiyama, M.; Hidaka, T.; Kohno, M.

1991-01-01

To elucidate the radical mechanism of lipid peroxidation induced by ultraviolet light (UV) irradiation, an electron spin resonance (ESR) study was made on epidermal homogenate prepared from albino rat skin. The exposure of the homogenate to UV light resulted in an increase in lipid peroxide content, which was proportional to the time of UV exposure. Using ESR spin trapping (dimethyl-1-pyrroline-N-oxide, DMPO), the DMPO spin adduct spectrum of lipid radicals (L.) was measured following UV exposure (DMPO-L.:aN = 15.5 G, aH = 22.7 G), as was the spectrum of DMPO-hydroxyl radical (DMPO-OH, aN = aH = 15.5 G). In the presence of superoxide dismutase, the DMPO spin adduct spectrum of lipid radicals was found to be reduced remarkably. Therefore, it was shown that the generation of the lipid radicals partially involves superoxide anion radicals, in addition to hydroxyl radicals. In the ESR free-radical experiment, an ESR signal appeared at g = 2.0064 when the ESR tube filled with homogenate was exposed to UV light at -150 degrees C. The temperature-dependent change in the ESR free radical signal of homogenate exposed to UV light was observed at temperatures varying from -150 degrees C to room temperature. By using degassed samples, it was confirmed that oxygen is involved in the formation of the lipid peroxide radicals (LOO.) from the lipid radicals (L.)

Reaction rate oscillations during catalytic CO oxidation: A brief overview

Science.gov (United States)

Tsotsis, T. T.; Sane, R. C.

1987-01-01

It is not the intent here to present a comprehensive review of the dynamic behavior of the catalytic oxidation of CO. This reaction is one of the most widely studied in the field of catalysis. A review paper by Engel and Ertl has examined the basic kinetic and mechanistic aspects, and a comprehensive paper by Razon and Schmitz was recently devoted to its dynamic behavior. Those interested in further study of the subject should consult these reviews and a number of general review papers on catalytic reaction dynamics. The goal is to present a brief overview of certain interesting aspects of the dynamic behavior of this reaction and to discuss a few questions and issues, which are still the subject of study and debate.

Morphological effects on the selectivity of intramolecular versus intermolecular catalytic reaction on Au nanoparticles.

Science.gov (United States)

Wang, Dan; Sun, Yuanmiao; Sun, Yinghui; Huang, Jing; Liang, Zhiqiang; Li, Shuzhou; Jiang, Lin

2017-06-14

It is hard for metal nanoparticle catalysts to control the selectivity of a catalytic reaction in a simple process. In this work, we obtain active Au nanoparticle catalysts with high selectivity for the hydrogenation reaction of aromatic nitro compounds, by simply employing spine-like Au nanoparticles. The density functional theory (DFT) calculations further elucidate that the morphological effect on thermal selectivity control is an internal key parameter to modulate the nitro hydrogenation process on the surface of Au spines. These results show that controlled morphological effects may play an important role in catalysis reactions of noble metal NPs with high selectivity.

Homogenization of tissues via picosecond-infrared laser (PIRL) ablation: Giving a closer view on the in-vivo composition of protein species as compared to mechanical homogenization.