Quantum catalysis : the modelling of catalytic transition states

NARCIS (Netherlands)

Hall, M.B.; Margl, P.; Naray-Szabo, G.; Schramm, Vern; Truhlar, D.G.; Santen, van R.A.; Warshel, A.; Whitten, J.L.; Truhlar, D.G.; Morokuma, K.

1999-01-01

A review with 101 refs.; we present an introduction to the computational modeling of transition states for catalytic reactions. We consider both homogeneous catalysis and heterogeneous catalysis, including organometallic catalysts, enzymes, zeolites and metal oxides, and metal surfaces. We summarize

DOE Laboratory Catalysis Research Symposium - Abstracts

Energy Technology Data Exchange (ETDEWEB)

Dunham, T.

1999-02-01

The conference consisted of two sessions with the following subtopics: (1) Heterogeneous Session: Novel Catalytic Materials; Photocatalysis; Novel Processing Conditions; Metals and Sulfides; Nuclear Magnetic Resonance; Metal Oxides and Partial Oxidation; Electrocatalysis; and Automotive Catalysis. (2) Homogeneous Catalysis: H-Transfer and Alkane Functionalization; Biocatalysis; Oxidation and Photocatalysis; and Novel Medical, Methods, and Catalyzed Reactions.

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.

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

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

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

Science.gov (United States)

Artero, Vincent; Fontecave, Marc

2013-03-21

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

Fundamental concepts in heterogeneous catalysis

CERN Document Server

Norskov, Jens K; Abild-Pedersen, Frank; Bligaard, Thomas

2014-01-01

This book is based on a graduate course and suitable as a primer for any newcomer to the field, this book is a detailed introduction to the experimental and computational methods that are used to study how solid surfaces act as catalysts.   Features include:First comprehensive description of modern theory of heterogeneous catalysisBasis for understanding and designing experiments in the field   Allows reader to understand catalyst design principlesIntroduction to important elements of energy transformation technologyTest driven at Stanford University over several semesters

Bridging heterogeneous and homogeneous catalysis concepts, strategies, and applications

CERN Document Server

Li, Can

2014-01-01

This unique handbook fills the gap in the market for an up-to-date work that links both homogeneous catalysis applied to organic reactions and catalytic reactions on surfaces of heterogeneous catalysts.

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.

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.

Density functional theory in surface science and heterogeneous catalysis

DEFF Research Database (Denmark)

Nørskov, Jens Kehlet; Scheffler, M.; Toulhoat, H.

2006-01-01

Solid surfaces are used extensively as catalysts throughout the chemical industry, in the energy sector, and in environmental protection. Recently, density functional theory has started providing new insight into the atomic-scale mechanisms of heterogeneous catalysis, helping to interpret the large...

International symposium on 'applications of zeolites in heterogeneous catalysis'

Energy Technology Data Exchange (ETDEWEB)

1978-11-01

The International Symposium on applications of zeolites in heterogeneous catalysis, organized by the Hungarian Chemical Society (Szeged, Hung. 9/11-14/78), included 48 papers, which were published in the Vertical Bar3Vertical BarActa Phys. Chem. (Szeged) 24.

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.

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

Combination of sunlight irradiated oxidative processes for landfill leachate: heterogeneous catalysis (TiO2 versus homogeneous catalysis (H2O2

Directory of Open Access Journals (Sweden)

Oswaldo Luiz Cobra Guimarães

2013-04-01

Full Text Available The objective of this work was to study the treatment of landfill leachate liquid in nature, after the use of a combination of advanced oxidation processes. More specifically, it compared heterogeneous catalysis with TiO2 to homogeneous catalysis with H2O2, both under photo-irradiated sunlight. The liquid used for the study was the leachate from the landfill of the city of Cachoeira Paulista, São Paulo State, Brazil. The experiments were conducted in a semi-batch reactor open to the absorption of solar UV radiation, with 120 min reaction time. The factors and their respective levels (-1, 0 and 1 were distributed in a experimental design 24-1 with duplicate and triplicate in the central point, resulting in an array with 19 treatment trials. The studied factors in comparing the two catalytic processes were: liquid leachate dilution, TiO2 concentration on the reactor plate, the H2O2 amount and pH level. The leachate had low photo-catalytic degradability, with NOPC reductions ranging from 1% to a maximum of 24.9%. When considering each factor alone, neither homogeneous catalysis with H2O2, nor heterogeneous catalysis with TiO2, could degrade the percolated liquid without significant reductions (5% level in total NOPC. On the other hand, the combined use of homogenous catalysis with H2O2 and heterogeneous catalysis H2O2 resulted in the greatest reductions in NOPC. The optimum condition for the NOPC reduction was obtained at pH 7, dilution of percolated:water at 1:1 (v v-1 rate; excess of 12.5% H2O2 and coating plate reactor with 0.025 g cm-2 TiO2.

ISHHC XIII International Symposium on the Relations betweenHomogeneous and Heterogeneous Catalysis

Energy Technology Data Exchange (ETDEWEB)

Somorjai (Ed.), G.A.

2007-06-11

The International Symposium on Relations between Homogeneous and Heterogeneous Catalysis (ISHHC) has a long and distinguished history. Since 1974, in Brussels, this event has been held in Lyon, France (1977), Groeningen, The Netherlands (1981); Asilomar, California (1983); Novosibirsk, Russia (1986); Pisa, Italy (1989); Tokyo, Japan (1992); Balatonfuered, Hungary (1995); Southampton, United Kingdom (1999); Lyon, France (2001); Evanston, Illinois (2001) and Florence, Italy (2005). The aim of this international conference in Berkeley is to bring together practitioners in the three fields of catalysis, heterogeneous, homogeneous and enzyme, which utilize mostly nanosize particles. Recent advances in instrumentation, synthesis and reaction studies permit the nanoscale characterization of the catalyst systems, often for the same reaction, under similar experimental conditions. It is hoped that this circumstance will permit the development of correlations of these three different fields of catalysis on the molecular level. To further this goal we aim to uncover and focus on common concepts that emerge from nanoscale studies of structures and dynamics of the three types of catalysts. Another area of focus that will be addressed is the impact on and correlation of nanosciences with catalysis. There is information on the electronic and atomic structures of nanoparticles and their dynamics that should have importance in catalyst design and catalytic activity and selectivity.

Biodiesel forming reactions using heterogeneous catalysis

Science.gov (United States)

Liu, Yijun

Biodiesel synthesis from biomass provides a means for utilizing effectively renewable resources, a way to convert waste vegetable oils and animal fats to a useful product, a way to recycle carbon dioxide for a combustion fuel, and production of a fuel that is biodegradable, non-toxic, and has a lower emission profile than petroleum-diesel. Free fatty acid (FFA) esterification and triglyceride (TG) transesterification with low molecular weight alcohols constitute the synthetic routes to prepare biodiesel from lipid feedstocks. This project was aimed at developing a better understanding of important fundamental issues involved in heterogeneous catalyzed biodiesel forming reactions using mainly model compounds, representing part of on-going efforts to build up a rational base for assay, design, and performance optimization of solid acids/bases in biodiesel synthesis. As FFA esterification proceeds, water is continuously formed as a byproduct and affects reaction rates in a negative manner. Using sulfuric acid (as a catalyst) and acetic acid (as a model compound for FFA), the impact of increasing concentrations of water on acid catalysis was investigated. The order of the water effect on reaction rate was determined to be -0.83. Sulfuric acid lost up to 90% activity as the amount of water present increased. The nature of the negative effect of water on esterification was found to go beyond the scope of reverse hydrolysis and was associated with the diminished acid strength of sulfuric acid as a result of the preferential solvation by water molecules of its catalytic protons. The results indicate that as esterification progresses and byproduct water is produced, deactivation of a Bronsted acid catalyst like H2SO4 occurs. Using a solid composite acid (SAC-13) as an example of heterogeneous catalysts and sulfuric acid as a homogeneous reference, similar reaction inhibition by water was demonstrated for homogeneous and heterogeneous catalysis. This similarity together with

Metal Catalysts for Heterogeneous Catalysis: From Single Atoms to Nanoclusters and Nanoparticles.

Science.gov (United States)

Liu, Lichen; Corma, Avelino

2018-05-23

Metal species with different size (single atoms, nanoclusters, and nanoparticles) show different catalytic behavior for various heterogeneous catalytic reactions. It has been shown in the literature that many factors including the particle size, shape, chemical composition, metal-support interaction, and metal-reactant/solvent interaction can have significant influences on the catalytic properties of metal catalysts. The recent developments of well-controlled synthesis methodologies and advanced characterization tools allow one to correlate the relationships at the molecular level. In this Review, the electronic and geometric structures of single atoms, nanoclusters, and nanoparticles will be discussed. Furthermore, we will summarize the catalytic applications of single atoms, nanoclusters, and nanoparticles for different types of reactions, including CO oxidation, selective oxidation, selective hydrogenation, organic reactions, electrocatalytic, and photocatalytic reactions. We will compare the results obtained from different systems and try to give a picture on how different types of metal species work in different reactions and give perspectives on the future directions toward better understanding of the catalytic behavior of different metal entities (single atoms, nanoclusters, and nanoparticles) in a unifying manner.

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.

Homogeneous Catalysis with Metal Complexes Fundamentals and Applications

CERN Document Server

Duca, Gheorghe

2012-01-01

The book about homogeneous catalysis with metal complexes deals with the description of the reductive-oxidative, metal complexes  in a liquid phase (in polar solvents, mainly in water, and less in nonpolar solvents). The exceptional importance of the redox processes in chemical systems, in the reactions occuring in living organisms, the environmental processes, atmosphere, water, soil, and in industrial technologies (especially in food-processing industries) is discussed. The detailed practical aspects of the established regularities are explained for solving the specific practical tasks in various fields of industrial chemistry, biochemistry, medicine, analytical chemistry and ecological chemistry. The main scope of the book is the survey and systematization of the latest advances in homogeneous catalysis with metal complexes. It gives an overview of the research results and practical experience accumulated by the author during the last decade.

Heterogeneous Catalysis: Understanding for Designing, and Designing for Applications

OpenAIRE

Corma Canós, Avelino

2016-01-01

Despite the introduction of high-throughput and combinatorial methods that certainly can be useful in the process of catalysts optimization, it is recognized that the generation of fundamental knowledge at the molecular level is key for the development of new concepts and for reaching the final objective of solid catalysts by design … Corma Canós, A. (2016). Heterogeneous Catalysis: Understanding for Designing, and Designing for Applications. Angewandte Chemie International Edition. 55(21)...

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.

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

Chemistry, spectroscopy and the role of supported vanadium oxides in heterogeneous catalysis

NARCIS (Netherlands)

Weckhuysen, B.M.; Keller, D.E.

2003-01-01

Supported vanadium oxide catalysts are active in a wide range of applications. In this review, an overview is given of the current knowledge available about vanadium oxide-based catalysts. The review starts with the importance of vanadium in heterogeneous catalysis, a discussion of the molecular

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.

Design of sintering-stable heterogeneous catalysts

DEFF Research Database (Denmark)

Gallas-Hulin, Agata

One of the major issues in the use of metal nanoparticles in heterogeneous catalysis is sintering. Sintering occurs at elevated temperatures because of increased mobility of nanoparticles, leading to their agglomeration and, as a consequence, to the deactivation of the catalyst. It is an emerging...... problem especially for the noble metals-based catalysis. These metals being expensive and scarce, it is worth developing catalyst systems which preserve their activity over time. Encapsulation of nanoparticles inside zeolites is one of the ways to prevent sintering. Entrapment of nanoparticles inside...

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.

Sustainable preparation of supported metal nanoparticles and their applications in catalysis.

Science.gov (United States)

Campelo, Juan M; Luna, Diego; Luque, Rafael; Marinas, José M; Romero, Antonio A

2009-01-01

Metal nanoparticles have attracted much attention over the last decade owing to their unique properties as compared to their bulk metal equivalents, including a large surface-to-volume ratio and tunable shapes. To control the properties of nanoparticles with particular respect to shape, size and dispersity is imperative, as these will determine the activity in the desired application. Supported metal nanoparticles are widely employed in catalysis. Recent advances in controlling the shape and size of nanoparticles have opened the possibility to optimise the particle geometry for enhanced catalytic activity, providing the optimum size and surface properties for specific applications. This Review describes the state of the art with respect to the preparation and use of supported metal nanoparticles in catalysis. The main groups of such nanoparticles (noble and transition metal nanoparticles) are highlighted and future prospects are discussed.

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 ...

Oxide-supported metal clusters: models for heterogeneous catalysts

International Nuclear Information System (INIS)

Santra, A K; Goodman, D W

2003-01-01

Understanding the size-dependent electronic, structural and chemical properties of metal clusters on oxide supports is an important aspect of heterogeneous catalysis. Recently model oxide-supported metal catalysts have been prepared by vapour deposition of catalytically relevant metals onto ultra-thin oxide films grown on a refractory metal substrate. Reactivity and spectroscopic/microscopic studies have shown that these ultra-thin oxide films are excellent models for the corresponding bulk oxides, yet are sufficiently electrically conductive for use with various modern surface probes including scanning tunnelling microscopy (STM). Measurements on metal clusters have revealed a metal to nonmetal transition as well as changes in the crystal and electronic structures (including lattice parameters, band width, band splitting and core-level binding energy shifts) as a function of cluster size. Size-dependent catalytic reactivity studies have been carried out for several important reactions, and time-dependent catalytic deactivation has been shown to arise from sintering of metal particles under elevated gas pressures and/or reactor temperatures. In situ STM methodologies have been developed to follow the growth and sintering kinetics on a cluster-by-cluster basis. Although several critical issues have been addressed by several groups worldwide, much more remains to be done. This article highlights some of these accomplishments and summarizes the challenges that lie ahead. (topical review)

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.

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.

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.

Titanium Dioxide as a Catalyst Support in Heterogeneous Catalysis

Science.gov (United States)

Bagheri, Samira; Muhd Julkapli, Nurhidayatullaili; Bee Abd Hamid, Sharifah

2014-01-01

The lack of stability is a challenge for most heterogeneous catalysts. During operations, the agglomeration of particles may block the active sites of the catalyst, which is believed to contribute to its instability. Recently, titanium oxide (TiO2) was introduced as an alternative support material for heterogeneous catalyst due to the effect of its high surface area stabilizing the catalysts in its mesoporous structure. TiO2 supported metal catalysts have attracted interest due to TiO2 nanoparticles high activity for various reduction and oxidation reactions at low pressures and temperatures. Furthermore, TiO2 was found to be a good metal oxide catalyst support due to the strong metal support interaction, chemical stability, and acid-base property. The aforementioned properties make heterogeneous TiO2 supported catalysts show a high potential in photocatalyst-related applications, electrodes for wet solar cells, synthesis of fine chemicals, and others. This review focuses on TiO2 as a support material for heterogeneous catalysts and its potential applications. PMID:25383380

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)

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)

Amino-functionalized metal-organic frameworks as tunable heterogeneous basic catalysts

Energy Technology Data Exchange (ETDEWEB)

Fischer, M.; Hartmann, M. [Erlangen-Nuernberg Univ., Erlangen (Germany). Erlangen Catalysis Resource Center

2011-07-01

Metal-organic framework (MOF) materials have been explored for applications in heterogeneous catalysis in recent years. In addition to the use of MOFs as supports for the deposition of highly dispersed metal particles, the incorporation of active centers such as coordinatively unsaturated metal sites and the functionalization of the organic linkers with acidic or basic groups seems to be most promising. In our contribution, three different MOFs carrying amino groups at their organic linkers, namely Fe-MIL-101-NH{sub 2} (S{sub BET} = 3438 m{sup 2}g{sup -1}), Al-MIL-101-NH{sub 2} (S{sub BET} = 3099 m{sup 2}g{sup -1}) and CAU-1 (S{sub BET} = 1492 m{sup 2}g{sup -1}), were synthesized and tested in the Knoevenagel condensation of benzaldehyde with malononitrile and with ethyl cyanoacetate, respectively. It is shown that the expected products benzylidenemalononitrile (BzMN) and ethyl a-cyanocinnamate (EtCC) are formed with selectivities of more than 99 % and yields of 90 to 95 % after 3 h (for BzMN). Due to the very small pore windows of CAU-1 (0.3 to 0.4 nm) the reaction proceeds much slower over this catalyst in comparison to the amino-MIL-101 derivatives, which possess open pore windows of up to 1.6 nm. Finally, leaching tests confirm that the reaction is heterogeneously catalyzed. Moreover, the catalysts are recyclable without significant loss of activity. (orig.)

Electroreduction of CO2 Catalyzed by a Heterogenized Zn–Porphyrin Complex with a Redox-Innocent Metal Center

Science.gov (United States)

2017-01-01

Transition-metal-based molecular complexes are a class of catalyst materials for electrochemical CO2 reduction to CO that can be rationally designed to deliver high catalytic performance. One common mechanistic feature of these electrocatalysts developed thus far is an electrogenerated reduced metal center associated with catalytic CO2 reduction. Here we report a heterogenized zinc–porphyrin complex (zinc(II) 5,10,15,20-tetramesitylporphyrin) as an electrocatalyst that delivers a turnover frequency as high as 14.4 site–1 s–1 and a Faradaic efficiency as high as 95% for CO2 electroreduction to CO at −1.7 V vs the standard hydrogen electrode in an organic/water mixed electrolyte. While the Zn center is critical to the observed catalysis, in situ and operando X-ray absorption spectroscopic studies reveal that it is redox-innocent throughout the potential range. Cyclic voltammetry indicates that the porphyrin ligand may act as a redox mediator. Chemical reduction of the zinc–porphyrin complex further confirms that the reduction is ligand-based and the reduced species can react with CO2. This represents the first example of a transition-metal complex for CO2 electroreduction catalysis with its metal center being redox-innocent under working conditions. PMID:28852698

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

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.

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

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.

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

Heterogeneous catalysis: on bathroom mirrors and boiling stones

NARCIS (Netherlands)

Philipse, A.P.

2011-01-01

A catalyst is defined as a substance that accelerates a process without undergoing a net change due to that process. Most chemistry students learn about catalysts in the context of chemical reactions, such as the enzymes in biochemistry or the heterogeneous metal catalysts in inorganic chemistry (1,

Electroreduction of CO ₂ Catalyzed by a Heterogenized Zn–Porphyrin Complex with a Redox-Innocent Metal Center

Energy Technology Data Exchange (ETDEWEB)

Wu, Yueshen [Department; Energy; Jiang, Jianbing [Department; Energy; Weng, Zhe [Department; Energy; Wang, Maoyu [School; Broere, Daniël L. J. [Department; Zhong, Yiren [Department; Energy; Brudvig, Gary W. [Department; Energy; Feng, Zhenxing [School; Wang, Hailiang [Department; Energy

2017-07-26

Transition-metal-based molecular complexes are a class of catalyst materials for electrochemical CO2 reduction to CO that can be rationally designed to deliver high catalytic performance. One common mechanistic feature of these electrocatalysts developed thus far is an electrogenerated reduced metal center associated with catalytic CO2 reduction. Here we report a heterogenized zinc–porphyrin complex (zinc(II) 5,10,15,20-tetramesitylporphyrin) as an electrocatalyst that delivers a turnover frequency as high as 14.4 site–1 s–1 and a Faradaic efficiency as high as 95% for CO2 electroreduction to CO at -1.7 V vs the standard hydrogen electrode in an organic/water mixed electrolyte. While the Zn center is critical to the observed catalysis, in situ and operando X-ray absorption spectroscopic studies reveal that it is redox-innocent throughout the potential range. Cyclic voltammetry indicates that the porphyrin ligand may act as a redox mediator. Chemical reduction of the zinc–porphyrin complex further confirms that the reduction is ligand-based and the reduced species can react with CO2. This represents the first example of a transition-metal complex for CO2 electroreduction catalysis with its metal center being redox-innocent under working conditions.

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)

Peripherally Metalated Porphyrins with Applications in Catalysis, Molecular Electronics and Biomedicine.

Science.gov (United States)

Longevial, Jean-François; Clément, Sébastien; Wytko, Jennifer A; Ruppert, Romain; Weiss, Jean; Richeter, Sébastien

2018-04-24

Porphyrins are conjugated, stable chromophores with a central core that binds a variety of metal ions and an easily functionalized peripheral framework. By combining the catalytic, electronic or cytotoxic properties of selected transition metal complexes with the binding and electronic properties of porphyrins, enhanced characteristics of the ensemble are generated. This review article focuses on porphyrins bearing one or more peripheral transition metal complexes and discusses their potential applications in catalysis or biomedicine. Modulation of the electronic properties and intramolecular communication through coordination bond linkages in bis-porphyrin scaffolds is also presented. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogen Production by Homogeneous Catalysis: Alcohol Acceptorless Dehydrogenation

DEFF Research Database (Denmark)

Nielsen, Martin

2015-01-01

in hydrogen production from biomass using homogeneous catalysis. Homogeneous catalysis has the advance of generally performing transformations at much milder conditions than traditional heterogeneous catalysis, and hence it constitutes a promising tool for future applications for a sustainable energy sector...

Biodiesel production through in situ transesterification of sunflower seeds by homogeneous and heterogeneous catalysis; Producao de biodiesel atraves de transesterificacao in situ de sementes de girassol via catalise homogenea e heterogenea

Energy Technology Data Exchange (ETDEWEB)

Fama, Paola Ervatti; San Gil, Rosane Aguiar da Silva; Lachter, Elizabeth Roditi, E-mail: lachter@iq.ufrj.b [Universidade Federal do Rio de Janeiro (IQ/UFRJ), RJ (Brazil). Inst. de Quimica

2010-07-01

The objective of this work is to show the results of the in situ transesterification of sunflower seed oil with methanol on basic homogeneous and heterogeneous catalysis for the production of biodiesel. In homogeneous catalysis, the activity of K{sub O}H and K{sub 2}CO{sub 3} were evaluated using the same oil:methanol ratio of 1:90. KOH showed to be more active than K2CO{sub 3}, leading to total conversion in biodiesel after 1h reaction time. In the heterogeneous catalysis the activity of K{sub 2}CO{sub 3}/Al{sub 2}O{sub 3} was comparable to the activity of K{sub 2}CO{sub 3} bulk: 53.0 and 66.6% resp. The properties of samples of biodiesel produced by homogeneous and heterogeneous catalysis were evaluated and are in accordance with the recommended fuel properties. (author)

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...

Synergy between experimental and theoretical methods in the exploration of homogeneous transition metal catalysis

DEFF Research Database (Denmark)

Lupp, Daniel; Christensen, Niels Johan; Fristrup, Peter

2014-01-01

n this Perspective, we will focus on the use of both experimental and theoretical methods in the exploration of reaction mechanisms in homogeneous transition metal catalysis. We briefly introduce the use of Hammett studies and kinetic isotope effects (KIE). Both of these techniques can be complem......n this Perspective, we will focus on the use of both experimental and theoretical methods in the exploration of reaction mechanisms in homogeneous transition metal catalysis. We briefly introduce the use of Hammett studies and kinetic isotope effects (KIE). Both of these techniques can...... be complemented by computational chemistry – in particular in cases where interpretation of the experimental results is not straightforward. The good correspondence between experiment and theory is only possible due to recent advances within the applied theoretical framework. We therefore also highlight...

Contributions to a rational design of heterogeneous catalysts: from experimentation to numerical simulation; Contributions a une conception rationnelle des catalyseurs heterogenes: de l'experimentation a la simulation numerique

Energy Technology Data Exchange (ETDEWEB)

Toulhoat, H

2002-03-01

I present through this dissertation a synthesis of my contributions to the field of heterogeneous catalysis, along two decades of research undertaken as a scientist at Institut Francais du Petrole. I started my itinerary on the 'floor', with the task of developing industrial hydro-treating catalysts, then I had the nice opportunity to lead advanced research on various subjects. However, I have been devoting myself for the past ten years to the encounter between catalysis and theoretical chemistry. The presentation of my work follows therefore a guideline starting with preparation and ending at modelization of the catalytic solid, after having gone through its characterization and the assessment of its activity. Modelization is thus founded on a consistent set of experimental informations. This guideline is applied to the four main themes to which this work is confined: hydro-treating catalysts, hydro-de-metallation catalysts, thio-resistance of noble metals, and solid acids. In summary, I believe I have contributed significantly, on the one hand to strong conceptual and technical advances in the area of ab initio simulation of elementary phenomena in heterogeneous catalysis, with the elaboration of original knowledge on catalysis by sulfides, metals and acids, as well as the genesis of alumina carriers, and on the other hand to a new approach of periodic trends in catalysis: this can be considered as a re-visitation of the principle of Sabatier, leading to a predictive tool for catalytic activity of solids. In a near future it will be possible to say if practical results validate this conceptual tool, and justify or not the ambitious title I gave to my work. (author)

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

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)

Contributions to a rational design of heterogeneous catalysts: from experimentation to numerical simulation; Contributions a une conception rationnelle des catalyseurs heterogenes: de l'experimentation a la simulation numerique

Energy Technology Data Exchange (ETDEWEB)

Toulhoat, H.

2002-03-01

I present through this dissertation a synthesis of my contributions to the field of heterogeneous catalysis, along two decades of research undertaken as a scientist at Institut Francais du Petrole. I started my itinerary on the 'floor', with the task of developing industrial hydro-treating catalysts, then I had the nice opportunity to lead advanced research on various subjects. However, I have been devoting myself for the past ten years to the encounter between catalysis and theoretical chemistry. The presentation of my work follows therefore a guideline starting with preparation and ending at modelization of the catalytic solid, after having gone through its characterization and the assessment of its activity. Modelization is thus founded on a consistent set of experimental informations. This guideline is applied to the four main themes to which this work is confined: hydro-treating catalysts, hydro-de-metallation catalysts, thio-resistance of noble metals, and solid acids. In summary, I believe I have contributed significantly, on the one hand to strong conceptual and technical advances in the area of ab initio simulation of elementary phenomena in heterogeneous catalysis, with the elaboration of original knowledge on catalysis by sulfides, metals and acids, as well as the genesis of alumina carriers, and on the other hand to a new approach of periodic trends in catalysis: this can be considered as a re-visitation of the principle of Sabatier, leading to a predictive tool for catalytic activity of solids. In a near future it will be possible to say if practical results validate this conceptual tool, and justify or not the ambitious title I gave to my work. (author)

Accurate Experimental and Theoretical Enthalpies of Association of TiCl4 with Typical Lewis Bases Used in Heterogeneous Ziegler-Natta Catalysis

KAUST Repository

Credendino, Raffaele; Minenkov, Yury; Liguori, Dario; Piemontesi, Fabrizio; Melchior, Andrea; Morini, Giampiero; Tolazzi, Marilena; Cavallo, Luigi

2017-01-01

Adducts of TiCl4 with Lewis bases used as internal or external donors in heterogeneous Ziegler-Natta (ZN) catalysis represents a fundamental interaction contributing to the final composition of MgCl2 supported ZN-catalysts. This study presents

Plasma-assisted heterogeneous catalysis for NOx reduction in lean-burn engine exhaust

Energy Technology Data Exchange (ETDEWEB)

Penetrante, B.M.; Hsaio, M.C.; Merritt, B.T.; Vogtlin, G.E. [Lawrence Livermore National Lab., CA (United States); Wan, C.Z.; Rice, G.W.; Voss, K.E. [Engelhard Corp., Iselin, NJ (United States)

1997-12-31

This paper discusses the combination of a plasma with a catalyst to improve the reduction of NO{sub x} under lean-burn conditions. The authors have been investigating the effects of a plasma on the NO{sub x} reduction activity and temperature operating window of various catalytic materials. One of the goals is to develop a fundamental understanding of the interaction between the gas-phase plasma chemistry and the heterogeneous chemistry on the catalyst surface. The authors have observed that plasma assisted heterogeneous catalysis can facilitate NO{sub x} reduction under conditions that normally make it difficult for either the plasma or the catalyst to function by itself. By systematically varying the plasma electrode and catalyst configuration, they have been able to elucidate the process by which the plasma chemistry affects the chemical reduction of NO{sub x} on the catalyst surface. They have discovered that the main effect of the plasma is to induce the gas-phase oxidation of NO to NO{sub 21}. The reduction of NO{sub x} to N{sub 2} is then accomplished by heterogeneous reaction of O with activated hydrocarbons on the catalyst surface. The use of a plasma opens the opportunity for a new class of catalysts that are potentially more durable, more active, more selective and more sulfur-tolerant compared to conventional lean-NO{sub x} catalysts.

Features of the kinetics of heterogeneous reactions with phase transformations on catalyst surfaces

Energy Technology Data Exchange (ETDEWEB)

Berman, A D; Krylov, O V

1978-01-01

This paper presents a review of 41 bibliographic references to experiments on the adsorption of various gases (e.g., carbon monoxide, formic acid, ammonia, and oxygen) on metals (e.g., nickel, molybdenum, and platinum) and oxides covers observations of two-dimensional phases during adsorption; the kinetics of adsorption and catalysis associated with two-dimensional phase transitions; and several approximate models for describing the kinetics of heterogeneous catalysis which account for two-dimensional phase transformations on catalyst surfaces.

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

Science.gov (United States)

Ye, Rong

be versatile scaffolds for the synthesis and stabilization of small nanoclusters. Then these dendrimer-encapsulated metal clusters (DEMCs) are adsorbed onto mesoporous silica. Through this method, we have achieved selective transformations that had been challenging to accomplish in a heterogeneous setting, e.g. pi-bond activation and aldol reactions. Extensive investigation into the catalytic systems under reaction conditions allowed us to correlate the structural features (e.g. oxidation states) of the catalysts and their activity. Moreover, we have demonstrated that supported DEMCs are also excellent catalysts for typical heterogeneous reactions, including hydrogenation and alkane isomerization. Critically, these investigations also confirmed that the supported DEMCs are heterogeneous and stable against leaching. Catalysts optimization is achieved through the modulation of various parameters. The clusters are oxidized (e.g., with PhICl2) or reduced (e.g., with H2) in situ. Changing the dendrimer properties (e.g., generation, terminal functional groups) is analogous to ligand modification in homogeneous catalysts, which affect both catalytic activity and selectivity. Similarly, pore size of the support is another factor in determining product distribution. In a flow reactor, the flow rate is adjusted to control the residence time of the starting material and intermediates, and thus the final product selectivity. Our approach to heterogeneous catalysis affords various advantages: (1) the catalyst system can tap into the reactivity typical to homogeneous catalysts, which conventional heterogeneous catalysts could not achieve; (2) unlike most homogeneous catalysts with comparable performance, the heterogenized homogeneous catalysts can be recycled; (3) improved activity or selectivity compared to conventional homogeneous catalysts is possible because of uniquely heterogeneous parameters for optimization. While localized surface plasmon resonance (LSPR) provides a

Major Successes of Theory-and-Experiment-Combined Studies in Surface Chemistry and Heterogeneous Catalysis.

Energy Technology Data Exchange (ETDEWEB)

Somorjai, Gabor A.; Li, Yimin

2009-11-21

Experimental discoveries followed by theoretical interpretations that pave the way of further advances by experimentalists is a developing pattern in modern surface chemistry and catalysis. The revolution of modern surface science started with the development of surface-sensitive techniques such as LEED, XPS, AES, ISS and SIMS, in which the close collaboration between experimentalists and theorists led to the quantitative determination of surface structure and composition. The experimental discovery of the chemical activity of surface defects and the trends in the reactivity of transitional metals followed by the explanations from the theoretical studies led to the molecular level understanding of active sites in catalysis. The molecular level knowledge, in turn, provided a guide for experiments to search for new generation of catalysts. These and many other examples of successes in experiment-and-theory-combined studies demonstrate the importance of the collaboration between experimentalists and theorists in the development of modern surface science.

Heterogeneous self-assembled media for biopolymerization

DEFF Research Database (Denmark)

Monnard, Pierre-Alain

2011-01-01

Heterogeneous media, such as micro-structured aqueous environments, could offer an alternative approach to the synthesis of biopolymers with novel functions. Structured media are here defined as specialized, self-assembled structures that are formed, e.g, by amphiphiles, such as liposomes, emulsion...... polymerization, the initial elongation rates clearly depended on the complementarity of the monomers with the templating nucleobases3. However, metal-ion catalyzed reactions deliver RNA analogs with heterogeneous linkages. Moreover, the usefulness of this medium in the form of quasi-compartmentalization extends...... beyond metal-ion catalysis reactions, as we have recently demonstrated the catalytic power of a dipeptide, SerHis, for the regioselective formation of phosphodiester bonds. These results in conjonction with the synthesis of nucleobases at -78˚C, the demonstration of ribozyme activity (RNA ligase ribozyme...

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.

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

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.

Heterogeneous Partial (ammOxidation and Oxidative Dehydrogenation Catalysis on Mixed Metal Oxides

Directory of Open Access Journals (Sweden)

Jacques C. Védrine

2016-01-01

Full Text Available This paper presents an overview of heterogeneous partial (ammoxidation and oxidative dehydrogenation (ODH of hydrocarbons. The review has been voluntarily restricted to metal oxide-type catalysts, as the partial oxidation field is very broad and the number of catalysts is quite high. The main factors of solid catalysts for such reactions, designated by Grasselli as the “seven pillars”, and playing a determining role in catalytic properties, are considered to be, namely: isolation of active sites (known to be composed of ensembles of atoms, Me–O bond strength, crystalline structure, redox features, phase cooperation, multi-functionality and the nature of the surface oxygen species. Other important features and physical and chemical properties of solid catalysts, more or less related to the seven pillars, are also emphasized, including reaction sensitivity to metal oxide structure, epitaxial contact between an active phase and a second phase or its support, synergy effect between several phases, acid-base aspects, electron transfer ability, catalyst preparation and activation and reaction atmospheres, etc. Some examples are presented to illustrate the importance of these key factors. They include light alkanes (C1–C4 oxidation, ethane oxidation to ethylene and acetic acid on MoVTe(SbNb-O and Nb doped NiO, propene oxidation to acrolein on BiMoCoFe-O systems, propane (ammoxidation to (acrylonitrile acrylic acid on MoVTe(SbNb-O mixed oxides, butane oxidation to maleic anhydride on VPO: (VO2P2O7-based catalyst, and isobutyric acid ODH to methacrylic acid on Fe hydroxyl phosphates. It is shown that active sites are composed of ensembles of atoms whose size and chemical composition depend on the reactants to be transformed (their chemical and size features and the reaction mechanism, often of Mars and van Krevelen type. An important aspect is the fact that surface composition and surface crystalline structure vary with reaction on stream until

Biopolymer-stabilized Pt nanoparticles colloid: a highly active and recyclable catalyst for biphasic catalysis

Energy Technology Data Exchange (ETDEWEB)

Wang, Yujia; Shen, Yueyue; Qiu, Yunfei; Zhang, Ting; Liao, Yang; Zhao, Shilin; Ma, Jun, E-mail: 1044208419@qq.com; Mao, Hui, E-mail: rejoice222@163.com [Sichuan Normal University, College of Chemistry and Materials Science (China)

2016-10-15

Noble metal nanoparticles are promising candidates to replace conventional bulk counterparts owing to their high activity and selectivity. To enable catalyst recovery, noble metal nanoparticles are often supported onto solid matrices to prepare heterogeneous catalyst. Although recycle of noble metal nanoparticles is realized by heterogenization, a loss of activity is usually encountered. In the present investigation, Pt nanoparticles with tunable particle size (1.85–2.80 nm) were facilely prepared by using polyphenols as amphiphilic stabilizers. The as-prepared Pt nanoparticles colloid solution could be used as highly active catalyst in aqueous–organic biphasic catalysis. The phenolic hydroxyls of polyphenols could constrain Pt nanoparticles in aqueous phase, and simultaneously, the aromatic scaffold of polyphenols ensured effective interactions between substrates and Pt nanoparticles. As a consequence, the obtained polyphenols-stabilized Pt nanoparticles exhibited high activity and cycling stability in biphasic hydrogenation of a series of unsaturated compounds. Compared with conventional heterogeneous Pt-C and Pt-Al{sub 2}O{sub 3} catalysts, polyphenols-stabilized Pt nanoparticles showed obvious advantage both in activity and cycling stability.

Biopolymer-stabilized Pt nanoparticles colloid: a highly active and recyclable catalyst for biphasic catalysis

International Nuclear Information System (INIS)

Wang, Yujia; Shen, Yueyue; Qiu, Yunfei; Zhang, Ting; Liao, Yang; Zhao, Shilin; Ma, Jun; Mao, Hui

2016-01-01

Noble metal nanoparticles are promising candidates to replace conventional bulk counterparts owing to their high activity and selectivity. To enable catalyst recovery, noble metal nanoparticles are often supported onto solid matrices to prepare heterogeneous catalyst. Although recycle of noble metal nanoparticles is realized by heterogenization, a loss of activity is usually encountered. In the present investigation, Pt nanoparticles with tunable particle size (1.85–2.80 nm) were facilely prepared by using polyphenols as amphiphilic stabilizers. The as-prepared Pt nanoparticles colloid solution could be used as highly active catalyst in aqueous–organic biphasic catalysis. The phenolic hydroxyls of polyphenols could constrain Pt nanoparticles in aqueous phase, and simultaneously, the aromatic scaffold of polyphenols ensured effective interactions between substrates and Pt nanoparticles. As a consequence, the obtained polyphenols-stabilized Pt nanoparticles exhibited high activity and cycling stability in biphasic hydrogenation of a series of unsaturated compounds. Compared with conventional heterogeneous Pt-C and Pt-Al 2 O 3 catalysts, polyphenols-stabilized Pt nanoparticles showed obvious advantage both in activity and cycling stability.

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.

The coalescence of heterogeneous liquid metal on nano substrate

Science.gov (United States)

Wang, Long; Li, Yifan; Zhou, Xuyan; Li, Tao; Li, Hui

2017-06-01

Molecular dynamics simulation has been performed to study the asymmetric coalescence of heterogeneous liquid metal on graphene. Simulation results show that the anomalies in the drop coalescence is mainly caused by the wettability of heterogeneous liquid metal. The silver atoms incline to distribute on the outer layer of the gold and copper droplets, revealing that the structure is determined by the interaction between different metal atoms. The coalescence and fusion of heterogeneous liquid metal drop can be predicted by comparing the wettability and the atomic mass of metallic liquid drops, which has important implications in the industrial application such as ink-jet printing and metallurgy.

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....

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.

Chiral phosphites as ligands in asymmetric metal complex catalysis and synthesis of coordination compounds

International Nuclear Information System (INIS)

Gavrilov, Konstantin N; Bondarev, Oleg G; Polosukhin, Aleksei I

2004-01-01

The data published during the last five years on the application of chiral derivatives of phosphorous acid in coordination chemistry and enantioselective catalysis are summarised and discussed. The effect of the nature of these ligands on the structure of metal complexes and on the efficiency of catalytic organic syntheses is shown. Hydroformylation, hydrogenation, allylic substitution and conjugate addition catalysed by transition metal complexes with optically active phosphites and hydrophosphoranes are considered. The prospects for the development of this field of research are demonstrated.

Metal-organic frameworks and their applications in catalysis; Redes metalorganicas e suas aplicacoes em catalise

Energy Technology Data Exchange (ETDEWEB)

Ramos, Andre Luis Dantas, E-mail: aldramos@ufs.br [Universidade Federal de Sergipe (UFSE), Sao Cristovao, SE (Brazil). Departamento de Engenharia Quimica; Tanase, Stefania; Rothenberg, Gadi [Van' t Hoff Institute for Molecular Sciences, University of Amsterdam, Amsterdam (Netherlands)

2014-07-01

Metal-organic frameworks (MOFs) form a new class of materials with well-defined yet tunable properties. These are crystalline, highly porous and exhibit strong metal-ligand interactions. Importantly, their physical and chemical properties, including pore size, pore structure, acidity, and magnetic and optical characteristics, can be tailored by choosing the appropriate ligands and metal precursors. Here we review the key aspects of synthesis and characterization of MOFs, focusing on lanthanide-based and vanadium-based materials. We also outline some of their applications in catalysis and materials science. (author)

Study of gas-liquid flow in model porous media for heterogeneous catalysis

Science.gov (United States)

Francois, Marie; Bodiguel, Hugues; Guillot, Pierre; Laboratory of the Future Team

2015-11-01

Heterogeneous catalysis of chemical reactions involving a gas and a liquid phase is usually achieved in fixed bed reactors. Four hydrodynamic regimes have been observed. They depend on the total flow rate and the ratio between liquid and gas flow rate. Flow properties in these regimes influence transfer rates. Rather few attempts to access local characterization have been proposed yet, though these seem to be necessary to better describe the physical mechanisms involved. In this work, we propose to mimic slices of reactor by using two-dimensional porous media. We have developed a two-dimensional system that is transparent to allow the direct observation of the flow and the phase distribution. While varying the total flow rate and the gas/liquid flow rate ratio, we observe two hydrodynamic regimes: at low flow rate, the gaseous phase is continuous (trickle flow), while it is discontinuous at higher flow rate (pulsed flow). Thanks to some image analysis techniques, we are able to quantify the local apparent liquid saturation in the system. Its fluctuations in time are characteristic of the transition between the two regimes: at low liquid flow rates, they are negligible since the liquid/gas interface is fixed, whereas at higher flow rates we observe an alternation between liquid and gas. This transition between trickle to pulsed flow is in relative good agreement with the existing state of art. However, we report in the pulsed regime important flow heterogeneities at the scale of a few pores. These heterogeneities are likely to have a strong influence on mass transfers. We acknowledge the support of Solvay.

High-density biosynthetic fuels: the intersection of heterogeneous catalysis and metabolic engineering.

Science.gov (United States)

Harvey, Benjamin G; Meylemans, Heather A; Gough, Raina V; Quintana, Roxanne L; Garrison, Michael D; Bruno, Thomas J

2014-05-28

Biosynthetic valencene, premnaspirodiene, and natural caryophyllene were hydrogenated and evaluated as high performance fuels. The parent sesquiterpenes were then isomerized to complex mixtures of hydrocarbons with the heterogeneous acid catalyst Nafion SAC-13. High density fuels with net heats of combustion ranging from 133-141 000 Btu gal(-1), or up to 13% higher than commercial jet fuel could be generated by this approach. The products of caryophyllene isomerization were primarily tricyclic hydrocarbons which after hydrogenation increased the fuel density by 6%. The isomerization of valencene and premnaspirodiene also generated a variety of sesquiterpenes, but in both cases the dominant product was δ-selinene. Ab initio calculations were conducted to determine the total electronic energies for the reactants and products. In all cases the results were in excellent agreement with the experimental distribution of isomers. The cetane numbers for the sesquiterpane fuels ranged from 20-32 and were highly dependent on the isomer distribution. Specific distillation cuts may have the potential to act as high density diesel fuels, while use of these hydrocarbons as additives to jet fuel will increase the range and/or time of flight of aircraft. In addition to the ability to generate high performance renewable fuels, the powerful combination of metabolic engineering and heterogeneous catalysis will allow for the preparation of a variety of sesquiterpenes with potential for pharmaceutical, flavor, and fragrance applications.

"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

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)

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

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.

Supported Ionic Liquid Phase (SILP) catalysis

DEFF Research Database (Denmark)

Riisager, Anders; Fehrmann, Rasmus; Haumann, Marco

2006-01-01

Applications of ionic liquids to replace conventional solvents in homogeneous transition-metal catalysis have increased significantly during the last decade. Biphasic ionic liquid/organic liquid systems offer advantages with regard to product separation, catalyst stability, and recycling...... but utilise in the case of fast chemical reactions only a small amount of expensive ionic liquid and catalyst. The novel Supported Ionic Liquid Phase (SILP) catalysis concept overcomes these drawbacks and allows the use of fixed-bed reactors for continuous reactions. In this Microreview the SILP catalysis...

Internal and Surface Phenomena in Heterogenous Metal Combustion

Science.gov (United States)

Dreizin, Edward L.

1997-01-01

The phenomenon of gas dissolution in burning metals was observed in recent metal combustion studies, but it could not be adequately explained by the traditional metal combustion models. The research reported here addresses heterogeneous metal combustion with emphasis on the processes of oxygen penetration inside burning metal and its influence on the metal combustion rate, temperature history, and disruptive burning. The unique feature of this work is the combination of the microgravity environment with a novel micro-arc generator of monodispersed metal droplets, ensuring repeatable formation and ignition of uniform metal droplets with a controllable initial temperature and velocity. Burning droplet temperature is measured in real time with a three wavelength pyrometer. In addition, particles are rapidly quenched at different combustion times, cross-sectioned, and examined using SEM-based techniques to retrieve the internal composition history of burning metal particles. When the initial velocity of a spherical particle is nearly zero, the microgravity environment makes it possible to study the flame structure, the development of flame nonsymmetry, and correlation of the flame shape with the heterogeneous combustion processes.

Catalytic olefin polymerization with early transition metal compounds

OpenAIRE

Eshuis, Johan Jan Willem

1991-01-01

The catalysis of organic reactions by soluble metal complexes has become a major tool in synthesis, both in the laboratory and in the chemical industry. Processes catalyzed by transition metal complexes include carbonylation, olefin polymerization, olefin addition, olefin oxidation and alkane and arene oxidation. Traditionally, heterogeneous catalysts have been used for the production of large-scale commodity chemicals such as methanol and ammonia and in the production of high octane gasoline...

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.

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.

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)

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.

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.

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...

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

Catalytic behavior of metal-organic frameworks and zeolites: Rationalization and comparative analysis

Czech Academy of Sciences Publication Activity Database

Opanasenko, Maksym

2015-01-01

Roč. 243, APR 2015 (2015), s. 2-9 ISSN 0920-5861 R&D Projects: GA ČR GA14-07101S Institutional support: RVO:61388955 Keywords : Metal -organic frameworks * Zeolites * heterogeneous catalysis Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.312, year: 2015

Synthesis of Alkanethiolate-Capped Metal Nanoparticles Using Alkyl Thiosulfate Ligand Precursors: A Method to Generate Promising Reagents for Selective Catalysis

Directory of Open Access Journals (Sweden)

Khin Aye San

2018-05-01

Full Text Available Evaluation of metal nanoparticle catalysts functionalized with well-defined thiolate ligands can be potentially important because such systems can provide a spatial control in the reactivity and selectivity of catalysts. A synthetic method utilizing Bunte salts (sodium S-alkylthiosulfates allows the formation of metal nanoparticles (Au, Ag, Pd, Pt, and Ir capped with alkanethiolate ligands. The catalysis studies on Pd nanoparticles show a strong correlation between the surface ligand structure/composition and the catalytic activity and selectivity for the hydrogenation/isomerization of alkenes, dienes, trienes, and allylic alcohols. The high selectivity of Pd nanoparticles is driven by the controlled electronic properties of the Pd surface limiting the formation of Pd–alkene adducts (or intermediates necessary for (additional hydrogenation. The synthesis of water soluble Pd nanoparticles using ω-carboxylate-S-alkanethiosulfate salts is successfully achieved and these Pd nanoparticles are examined for the hydrogenation of various unsaturated compounds in both homogeneous and heterogeneous environments. Alkanethiolate-capped Pt nanoparticles are also successfully synthesized and further investigated for the hydrogenation of various alkynes to understand their geometric and electronic surface properties. The high catalytic activity of activated terminal alkynes, but the significantly low activity of internal alkynes and unactivated terminal alkynes, are observed for Pt nanoparticles.

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.

Final Technical Report for DOE Grant DE-FG02-03ER15473 ''Molecular Level Design of Heterogeneous Chiral Catalysis''

International Nuclear Information System (INIS)

David Sholl; Andrew Gellman

2007-01-01

The production of enantiomerically pure chiral compounds is of great importance in the pharmaceutical industry. Although processes involving chiral catalysis and separations involving solid surfaces are known, the molecular-scale details of these processes are not well understood. This lack of understanding strongly limits the development of new chiral processes. Our collaborative research effort examines several intertwined aspects of chirality and enantioselectivity at catalytically active metal surfaces. At Carnegie Mellon, our efforts focus on the development of chirally imprinted metal powders as materials for chiral columns and the experimental and theoretical study of small chiral molecules adsorbed on well-characterized metal surfaces, both achiral and chiral. These efforts are being performed in close collaboration with our team members at the University of California Riverside and the University of Wisconsin Milwaukee

Luminescent Lanthanide Metal Organic Frameworks for cis-Selective Isoprene Polymerization Catalysis

Directory of Open Access Journals (Sweden)

Samantha Russell

2015-11-01

Full Text Available In this study, we are combining two areas of chemistry; solid-state coordination polymers (or Metal-Organic Framework—MOF and polymerization catalysis. MOF compounds combining two sets of different lanthanide elements (Nd3+, Eu3+/Tb3+ were used for that purpose: the use of neodymium was required due to its well-known catalytic properties in dienes polymerization. A second lanthanide, europium or terbium, was included in the MOF structure with the aim to provide luminescent properties. Several lanthanides-based MOF meeting these criteria were prepared according to different approaches, and they were further used as catalysts for the polymerization of isoprene. Stereoregular cis-polyisoprene was received, which in some cases exhibited luminescent properties in the UV-visible range.

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

Chemical bonding of water to metal surfaces studied with core-level spectroscopies

DEFF Research Database (Denmark)

Schiros, T.; Andersson, Klas Jerker; Pettersson, L.G.M.

2010-01-01

The nature of the contact layer of water on surfaces is of relevance for many practical fields, including corrosion, electrochemistry, environmental science and heterogeneous catalysis. Here we focus on the geometric and electronic structure of the water contact layer on transition metal surfaces......-specific information on the partial local density of states, local atomic structure, geometrical parameters and molecular orientation, allowing general principles for water-metal interaction to be derived....

Current advances and trends in electro-Fenton process using heterogeneous catalysts - A review.

Science.gov (United States)

Poza-Nogueiras, Verónica; Rosales, Emilio; Pazos, Marta; Sanromán, M Ángeles

2018-06-01

Over the last decades, advanced oxidation processes have often been used alone, or combined with other techniques, for remediation of ground and surface water pollutants. The application of heterogeneous catalysis to electrochemical advanced oxidation processes is especially useful due to its efficiency and environmental safety. Among those processes, electro-Fenton stands out as the one in which heterogeneous catalysis has been broadly applied. Thus, this review has introduced an up-to-date collation of the current knowledge of the heterogeneous electro-Fenton process, highlighting recent advances in the use of different catalysts such as iron minerals (pyrite, magnetite or goethite), prepared catalysts by the load of metals in inorganic and organic materials, nanoparticles, and the inclusion of catalysts on the cathode. The effects of physical-chemical parameters as well as the mechanisms involved are critically assessed. Finally, although the utilization of this process to remediation of wastewater overwhelmingly outnumber other utilities, several applications have been described in the context of regeneration of adsorbent or the remediation of soils as clear examples of the feasibility of the electro-Fenton process to solve different environmental problems. Copyright © 2018 Elsevier Ltd. All rights reserved.

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...

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.

The Sabatier Principle Illustrated by Catalytic H2O2 Decomposition on Metal Surfaces

DEFF Research Database (Denmark)

Laursen, Anders Bo; Man, Isabela Costinela; Trinhammer, Ole

2011-01-01

Heterogeneous catalysis is important in today’s industry. Hence, it is imperative to introduce students to this field and its tools. A new way of introducing one of these tools, the Sabatier principle, via a laboratory exercise is presented. A volcano plot is constructed for the well-known hetero......Heterogeneous catalysis is important in today’s industry. Hence, it is imperative to introduce students to this field and its tools. A new way of introducing one of these tools, the Sabatier principle, via a laboratory exercise is presented. A volcano plot is constructed for the well......-known heterogeneous H2O2 catalytic decomposition reaction on various metal foils. The activity per catalyst surface area versus the computationally calculated binding energy of OH groups on the catalysts is plotted. The OH group is identified as the only surface intermediate in an intuitive reaction mechanism...

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.

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)

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

Pincer-porphyrin hybrids : Synthesis, self-assembly, and catalysis

NARCIS (Netherlands)

Suijkerbuijk, B.M.J.M.

2007-01-01

Metal complexes play an important role in established research areas such as catalysis and materials chemistry as well as in emerging fields of chemical exploration such as bioinorganic chemistry. Changes in the metal center's ligand environment, i.e., the nature and number of the Lewis basic atoms

Noble Metal Immersion Spectroscopy of Silica Alcogels and Aerogels

Science.gov (United States)

Smith, David D.; Sibille, Laurent; Cronise, Raymond J.; Noever, David A.

1998-01-01

We have fabricated aerogels containing gold and silver nanoparticles for gas catalysis applications. By applying the concept of an average or effective dielectric constant to the heterogeneous interlayer surrounding each particle, we extend the technique of immersion spectroscopy to porous or heterogeneous media. Specifically, we apply the predominant effective medium theories for the determination of the average fractional composition of each component in this inhomogeneous layer. Hence, the surface area of metal available for catalytic gas reaction is determined. The technique is satisfactory for statistically random metal particle distributions but needs further modification for aggregated or surfactant modified systems. Additionally, the kinetics suggest that collective particle interactions in coagulated clusters are perturbed during silica gelation resulting in a change in the aggregate geometry.

Surface Plasmon Resonance Evaluation of Colloidal Metal Aerogel Filters

Science.gov (United States)

Smith, David D.; Sibille, Laurent; Cronise, Raymond J.; Noever, David A.

1997-01-01

We have fabricated aerogels containing gold, silver, and platinum nanoparticles for gas catalysis applications. By applying the concept of an average or effective dielectric constant to the heterogeneous interlayer surrounding each particle, we extend the technique of immersion spectroscopy to porous or heterogeneous media. Specifically, we apply the predominant effective medium theories for the determination of the average fractional composition of each component in this inhomogeneous layer. Hence, the surface area of metal available for catalytic gas reaction is determined. The technique is satisfactory for statistically random metal particle distributions but needs further modification for aggregated or surfactant modified systems. Additionally, the kinetics suggest that collective particle interactions in coagulated clusters are perturbed during silica gelation resulting in a change in the aggregate geometry.

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.

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.

A new class of PN3-pincer ligands for metal–ligand cooperative catalysis

KAUST Repository

Li, Huaifeng

2014-12-01

Work on a new class of PN3-pincer ligands for metal-ligand cooperative catalysis is reviewed. While the field of the pyridine-based PN3-transition metal pincer complexes is still relatively young, many important applications of these complexes have already emerged. In several cases, the PN3-pincer complexes for metal-ligand cooperative catalysis result in significantly improved or unprecedented activities. The synthesis and coordination chemistry of PN3-pincer ligands are briefly summarized first to cover the synthetic routes for their preparation, followed by a focus review on their applications in catalysis. A specific emphasis is placed on the later section about the role of PN3-pincer ligands\\' dearomatization-rearomatization steps during the catalytic cycles. The mechanistic insights from density functional theory (DFT) calculations are also discussed.

A new class of PN3-pincer ligands for metal–ligand cooperative catalysis

KAUST Repository

Li, Huaifeng; Zheng, Bin; Huang, Kuo-Wei

2014-01-01

Work on a new class of PN3-pincer ligands for metal-ligand cooperative catalysis is reviewed. While the field of the pyridine-based PN3-transition metal pincer complexes is still relatively young, many important applications of these complexes have already emerged. In several cases, the PN3-pincer complexes for metal-ligand cooperative catalysis result in significantly improved or unprecedented activities. The synthesis and coordination chemistry of PN3-pincer ligands are briefly summarized first to cover the synthetic routes for their preparation, followed by a focus review on their applications in catalysis. A specific emphasis is placed on the later section about the role of PN3-pincer ligands' dearomatization-rearomatization steps during the catalytic cycles. The mechanistic insights from density functional theory (DFT) calculations are also discussed.

Titanium oxide modification with oxides of mixed cobalt valence for photo catalysis

International Nuclear Information System (INIS)

Alanis O, R.; Jimenez B, J.

2010-01-01

In the present work, heterogenous photo catalysis, a technique often used for organic compound degradation toxic in water, was used. The photo catalyst most often used in this technique is TiO 2 , which due to its physical and chemical properties, can degrade a great number of organic compounds. In addition, in recent years it has been verified that the doping of semiconductors with metals or metallic oxides increases the photo catalytic activity of these semiconductors, which is why it was proposed for doping by the impregnating method using commercial TiO 2 synthesized by the Degussa company (TiO 2 Degussa P25) with and oxide of mixed cobalt valence (Co 3 O 4 ) synthesized using the sol-gel method. The synthesized photo catalyst TiO 2 /Co 3 O 4 was characterized by the techniques of X-ray diffraction, scanning electronic microscopy, Raman spectroscopy and finally, photo catalytic tests by means of the degradation of methylene blue. (Author)

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

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

Yolk-shell gold nanoparticles as model materials for support-effect studies in heterogeneous catalysis: Au, @C and Au, @ZrO2 for CO oxidation as an example.

Science.gov (United States)

Galeano, Carolina; Güttel, Robert; Paul, Michael; Arnal, Pablo; Lu, An-Hui; Schüth, Ferdi

2011-07-18

The use of nanostructured yolk-shell materials offers a way to discriminate support and particle-size effects for mechanistic studies in heterogeneous catalysis. Herein, gold yolk-shell materials have been synthesized and used as model catalysts for the investigation of support effects in CO oxidation. Carbon has been selected as catalytically inert support to study the intrinsic activity of the gold nanoparticles, and for comparison, zirconia has been used as oxidic support. Au, @C materials have been synthesized through nanocasting using two different nonporous-core@mesoporous-shell exotemplates: Au@SiO(2)@ZrO(2) and Au@SiO(2)@m-SiO(2). The catalytic activity of Au, @C with a gold core of about 14 nm has been evaluated and compared with Au, @ZrO(2) of the same gold core size. The strong positive effect of metal oxide as support material on the activity of gold has been proved. Additionally, size effects were investigated using carbon as support to determine only the contribution of the nanoparticle size on the catalytic activity of gold. Therefore, Au, @C with a gold core of about 7 nm was studied showing a less pronounced positive effect on the activity than the metal oxide support effect. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

ESR study into mechanism of heterogeneous-catalytic oxidation on oxides

Energy Technology Data Exchange (ETDEWEB)

Topchieva, K V; Loginov, A Yu; Kostikov, S V [Moskovskij Gosudarstvennyj Univ. (USSR)

1977-12-11

The role of radical particles in heterogeneous-catalytic oxidation of H/sub 2/; CO; SO/sub 2/; NH/sub 3/; C/sub 3/H/sub 6/ on the rare earth oxides (yttrium, lanthanum, magnesium and scandium oxides) and alkaline earth metal oxides was studied by the ESR method. The conclusion was made about the great reactivity of the peroxide structures O/sub 2//sup -/ in the oxidation catalysis in comparison to other formulas of chemisorption oxigen on oxides. The kinetic investigations are chemisorption oxigen on oxides. The kinetic investigations are carried out on the change of the concentration of paramagnetic particles O/sub 2/ during the catalysis. On the basis of the received data the conclusion is made about the reaction process of catalytic oxidation on rare and alkaline-earth oxides according to radical-chain mechanism with the formation of radical particles O/sub 2//sup -/, CO/sub 3//sup -/, SO/sub 4//sup -/, CO/sub 2//sup -/ as interediate products.

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)

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...

Effect of catalysts on heterogeneous oxidation of coal

Energy Technology Data Exchange (ETDEWEB)

Glazkova, A P; Kazarova, Yu A; Suslov, A V

1978-01-01

Analyzes the effects of catalysts on the heterogeneous oxidation of coal in deflagration processes of stoichiometric mixtures. The following substances are studied as catalysts: alkali and alkaline-earth metals, and compounds of copper, lead, chromium, iron, and sulfur. In the first case the catalysts are used in the form of nitrates and the nitrate simultaneously plays the role of an oxidizer. In the second case the catalysts are added to stoichiometric mixtures of ammonium nitrate with carbon. It is shown that during carbon oxidation by nitrates the catalytic efficiency of the metals studied forms the following order: sodium > lead > potassium > barium > aluminium > calcium > magnesium > copper. The calculated and experimental parameters of combustion are given. The problem of dependence of combustion rate on combustion heat, the mechanism of the combustion reaction and the catalytic effects of the additives are discussed. Features of heterogeneous catalysis in the oxidation process of carbon by various oxidizers are analyzed. The investigations on the combustion process are important as the process takes place during explosion of coal dust in underground coal mines and during burning of coal in industrial furnaces. (34 refs.) (In Russian)

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)

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.

Charge Transfer and Support Effects in Heterogeneous Catalysis

Energy Technology Data Exchange (ETDEWEB)

Hervier, Antoine [Univ. of California, Berkeley, CA (United States)

2011-12-21

CO oxidation conditions, the O1s spectrum showed a high binding energy peak that correlated in intensity with the activity of the different films: for stoichiometric films, the peak decreased in intensity with F-doping, while for nonstoichiometric films, the opposite was observed. No such changes were visible in the C1s spectrum, confirming the role of O activation in the reaction. This thesis adds to the body of knowledge on the importance of charge transfer at the metal-oxide interface in shaping the reactivity of heterogeneous catalysts, and provides examples of how this can be the basis for new methods to tune reactivity.

Titanium oxide modification with oxides of mixed cobalt valence for photo catalysis

Energy Technology Data Exchange (ETDEWEB)

Alanis O, R.; Jimenez B, J., E-mail: jaime.jimenez@inin.gob.m [ININ, Departamento de Quimica, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico)

2010-07-01

In the present work, heterogenous photo catalysis, a technique often used for organic compound degradation toxic in water, was used. The photo catalyst most often used in this technique is TiO{sub 2}, which due to its physical and chemical properties, can degrade a great number of organic compounds. In addition, in recent years it has been verified that the doping of semiconductors with metals or metallic oxides increases the photo catalytic activity of these semiconductors, which is why it was proposed for doping by the impregnating method using commercial TiO{sub 2} synthesized by the Degussa company (TiO{sub 2} Degussa P25) with and oxide of mixed cobalt valence (Co{sub 3}O{sub 4}) synthesized using the sol-gel method. The synthesized photo catalyst TiO{sub 2}/Co{sub 3}O{sub 4} was characterized by the techniques of X-ray diffraction, scanning electronic microscopy, Raman spectroscopy and finally, photo catalytic tests by means of the degradation of methylene blue. (Author)

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

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

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...

Monodisperse Platinum and Rhodium Nanoparticles as Model Heterogeneous Catalysts

Energy Technology Data Exchange (ETDEWEB)

Grass, Michael Edward [Univ. of California, Berkeley, CA (United States)

2008-09-01

Model heterogeneous catalysts have been synthesized and studied to better understand how the surface structure of noble metal nanoparticles affects catalytic performance. In this project, monodisperse rhodium and platinum nanoparticles of controlled size and shape have been synthesized by solution phase polyol reduction, stabilized by polyvinylpyrrolidone (PVP). Model catalysts have been developed using these nanoparticles by two methods: synthesis of mesoporous silica (SBA-15) in the presence of nanoparticles (nanoparticle encapsulation, NE) to form a composite of metal nanoparticles supported on SBA-15 and by deposition of the particles onto a silicon wafer using Langmuir-Blodgett (LB) monolayer deposition. The particle shapes were analyzed by transmission electron microscopy (TEM) and high resolution TEM (HRTEM) and the sizes were determined by TEM, X-ray diffraction (XRD), and in the case of NE samples, room temperature H₂ and CO adsorption isotherms. Catalytic studies were carried out in homebuilt gas-phase reactors. For the nanoparticles supported on SBA-15, the catalysts are in powder form and were studied using the homebuilt systems as plug-flow reactors. In the case of nanoparticles deposited on silicon wafers, the same systems were operated as batch reactors. This dissertation has focused on the synthesis, characterization, and reaction studies of model noble metal heterogeneous catalysts. Careful control of particle size and shape has been accomplished though solution phase synthesis of Pt and Rh nanoparticles in order to elucidate further structure-reactivity relationships in noble metal catalysis.

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...

Modified silica-based heterogeneous catalysts for etherification of glycerol

Energy Technology Data Exchange (ETDEWEB)

Gholami, Zahra, E-mail: zahra.gholami@petronas.com.my [Centralized Analytical Laboratory, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750 Tronoh, Perak (Malaysia); Abdullah, Ahmad Zuhairi, E-mail: chzuhairi@usm.my; Gholami, Fatemeh, E-mail: fgholami59@gmail.com [School of Chemical Engineering, Universiti Sains Malaysia, Engineering Campus,14300 Nibong Tebal, Penang (Malaysia); Vakili, Mohammadtaghi, E-mail: farshid3601@gmail.com [School of Industrial Technology, Universiti Sains Malaysia, 11800 Penang (Malaysia)

2015-07-22

The advent of mesoporous silicas such as MCM-41 has provided new opportunities for research into supported metal catalysis. The loading of metals into framework structures and particularly into the pores of porous molecular sieves, has long been of interest because of their potential catalytic activity. Stable heterogeneous mesoporous basic catalysts were synthesized by wet impregnation of MCM-41 with calcium nitrate and lanthanum nitrate. The surface and structural properties of the prepared catalysts were characterized using BET surface analysis, SEM and TEM. MCM-41 and modified MCM-41 were used in the solventless etherification of glycerol to produce diglycerol as the desired product. The reaction was performed at 250 °C for 8 h, and catalyst activity was evaluated. Catalytic etherification over the 20%Ca{sub 1.6}La{sub 0.6}/MCM-41 catalyst resulted in the highest glycerol conversion of 91% and diglycerol yield of 43%.

Modified silica-based heterogeneous catalysts for etherification of glycerol

International Nuclear Information System (INIS)

Gholami, Zahra; Abdullah, Ahmad Zuhairi; Gholami, Fatemeh; Vakili, Mohammadtaghi

2015-01-01

The advent of mesoporous silicas such as MCM-41 has provided new opportunities for research into supported metal catalysis. The loading of metals into framework structures and particularly into the pores of porous molecular sieves, has long been of interest because of their potential catalytic activity. Stable heterogeneous mesoporous basic catalysts were synthesized by wet impregnation of MCM-41 with calcium nitrate and lanthanum nitrate. The surface and structural properties of the prepared catalysts were characterized using BET surface analysis, SEM and TEM. MCM-41 and modified MCM-41 were used in the solventless etherification of glycerol to produce diglycerol as the desired product. The reaction was performed at 250 °C for 8 h, and catalyst activity was evaluated. Catalytic etherification over the 20%Ca 1.6 La 0.6 /MCM-41 catalyst resulted in the highest glycerol conversion of 91% and diglycerol yield of 43%

Reactor for in situ measurements of spatially resolved kinetic data in heterogeneous catalysis

Science.gov (United States)

Horn, R.; Korup, O.; Geske, M.; Zavyalova, U.; Oprea, I.; Schlögl, R.

2010-06-01

The present work describes a reactor that allows in situ measurements of spatially resolved kinetic data in heterogeneous catalysis. The reactor design allows measurements up to temperatures of 1300 °C and 45 bar pressure, i.e., conditions of industrial relevance. The reactor involves reactants flowing through a solid catalyst bed containing a sampling capillary with a side sampling orifice through which a small fraction of the reacting fluid (gas or liquid) is transferred into an analytical device (e.g., mass spectrometer, gas chromatograph, high pressure liquid chromatograph) for quantitative analysis. The sampling capillary can be moved with μm resolution in or against flow direction to measure species profiles through the catalyst bed. Rotation of the sampling capillary allows averaging over several scan lines. The position of the sampling orifice is such that the capillary channel through the catalyst bed remains always occupied by the capillary preventing flow disturbance and fluid bypassing. The second function of the sampling capillary is to provide a well which can accommodate temperature probes such as a thermocouple or a pyrometer fiber. If a thermocouple is inserted in the sampling capillary and aligned with the sampling orifice fluid temperature profiles can be measured. A pyrometer fiber can be used to measure the temperature profile of the solid catalyst bed. Spatial profile measurements are demonstrated for methane oxidation on Pt and methane oxidative coupling on Li/MgO, both catalysts supported on reticulated α -Al2O3 foam supports.

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

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

Precipitation of heterogeneous nanostructures: Metal nanoparticles and dielectric nanocrystallites

International Nuclear Information System (INIS)

Masai, Hirokazu; Takahashi, Yoshihiro; Fujiwara, Takumi; Tokuda, Yomei; Yoko, Toshinobu

2010-01-01

Heterogeneous precipitation of nanocrystallites of metallic Bi and anatase was observed in CaO-Bi 2 O 3 -B 2 O 3 -Al 2 O 3 -TiO 2 glass-ceramics. Addition of AlN reduced the Bi 2 O 3 to Bi metal nanoparticles, which were uniformly dispersed in the glass. After heat-treatment of the Bi-precipitated glass around the glass transition temperature, nanocrystalline anatase precipitated out without aggregation of the Bi metal particles. It was found that the anatase nanocrystal size was affected by the distance between a nanocrystal and a precipitated Bi nanoparticle. The glass-ceramic produced is a functional material containing a random dispersion of different types of nanoparticles with different dielectric constants.

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.

Modulation of individual steps in group I intron catalysis by a peripheral metal ion.

Science.gov (United States)

Forconi, Marcello; Piccirilli, Joseph A; Herschlag, Daniel

2007-10-01

Enzymes are complex macromolecules that catalyze chemical reactions at their active sites. Important information about catalytic interactions is commonly gathered by perturbation or mutation of active site residues that directly contact substrates. However, active sites are engaged in intricate networks of interactions within the overall structure of the macromolecule, and there is a growing body of evidence about the importance of peripheral interactions in the precise structural organization of the active site. Here, we use functional studies, in conjunction with published structural information, to determine the effect of perturbation of a peripheral metal ion binding site on catalysis in a well-characterized catalytic RNA, the Tetrahymena thermophila group I ribozyme. We perturbed the metal ion binding site by site-specifically introducing a phosphorothioate substitution in the ribozyme's backbone, replacing the native ligands (the pro-R (P) oxygen atoms at positions 307 and 308) with sulfur atoms. Our data reveal that these perturbations affect several reaction steps, including the chemical step, despite the absence of direct contacts of this metal ion with the atoms involved in the chemical transformation. As structural probing with hydroxyl radicals did not reveal significant change in the three-dimensional structure upon phosphorothioate substitution, the effects are likely transmitted through local, rather subtle conformational rearrangements. Addition of Cd(2+), a thiophilic metal ion, rescues some reaction steps but has deleterious effects on other steps. These results suggest that native interactions in the active site may have been aligned by the naturally occurring peripheral residues and interactions to optimize the overall catalytic cycle.

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...

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...

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)

Real-Time Monitoring of Heterogeneous Catalysis with Mass Spectrometry

Science.gov (United States)

Young, Mark A.

2009-01-01

Heterogeneous, gas-solid processes constitute an important class of catalytic reactions that play a key role in a variety of applications, such as industrial processing and environmental controls. Heterogeneous catalytic chemistry can be demonstrated in a simple heated flow reactor containing a fragment of the catalytic converter from a vehicular…

On the compensation effect in heterogeneous catalysis

DEFF Research Database (Denmark)

Pedersen, Thomas Bligaard; Honkala, Johanna Karoliina; Logadottir, Ashildur

2003-01-01

For a class of heterogeneously catalyzed reactions, we explain the compensation effect in terms of a switching of kinetic regimes leading to a concomitant change in the apparent activation energy and in the prefactor for the overall rate of the reaction. We first use the ammonia synthesis...

Sulfation of metal-organic framework: Opportunities for acid catalysis and proton conductivity

Energy Technology Data Exchange (ETDEWEB)

Goesten, M.G.; Stavitski, E.; Juan-Alcaniz, J.; Ramos-Fernandez, E.V.; Sai Sankar Gupta, K.B.; van Bekkum, H.; Gascon, J. and Kapteijn, F.

2011-05-24

A new post-functionalization method for metal-organic frameworks (MOFs) has been developed to introduce acidity for catalysis. Upon treatment with a mixture of triflic anhydride and sulfuric acid, chemically stable MOF structures MIL-101(Cr) and MIL-53(Al) can be sulfated, resulting in a Broensted sulfoxy acid group attached to up to 50% of the aromatic terephthalate linkers of the structure. The sulfated samples have been extensively characterized by solid-state NMR, XANES, and FTIR spectroscopy. The functionalized acidic frameworks show catalytic activity similar to that of acidic polymers like Nafion{reg_sign} display in the esterification of n-butanol with acetic acid (TOF {approx} 1 min{sup -1} {at} 343 K). Water adsorbs strongly up to 4 molecules per sulfoxy acid group, and an additional 2 molecules are taken up at lower temperatures in the 1-D pore channels of S-MIL-53(Al). The high water content and Broensted acidity provide the structure S-MIL-53(Al) a high proton conductivity up to moderate temperatures.

Electrical Matching at Metal/Molecule Contacts for Efficient Heterogeneous Charge Transfer.

Science.gov (United States)

Sato, Shino; Iwase, Shigeru; Namba, Kotaro; Ono, Tomoya; Hara, Kenji; Fukuoka, Atsushi; Uosaki, Kohei; Ikeda, Katsuyoshi

2018-02-27

In a metal/molecule hybrid system, unavoidable electrical mismatch exists between metal continuum states and frontier molecular orbitals. This causes energy loss in the electron conduction across the metal/molecule interface. For efficient use of energy in a metal/molecule hybrid system, it is necessary to control interfacial electronic structures. Here we demonstrate that electrical matching between a gold substrate and π-conjugated molecular wires can be obtained by using monatomic foreign metal interlayers, which can change the degree of d-π* back-donation at metal/anchor contacts. This interfacial control leads to energy level alignment between the Fermi level of the metal electrode and conduction molecular orbitals, resulting in resonant electron conduction in the metal/molecule hybrid system. When this method is applied to molecule-modified electrocatalysts, the heterogeneous electrochemical reaction rate is considerably improved with significant suppression of energy loss at the internal electron conduction.

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.

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

Spatial coupling in heterogeneous catalysis

Science.gov (United States)

Yamamoto, S. Y.; Surko, C. M.; Maple, M. B.

1995-11-01

Spatial coupling mechanisms are studied in the heterogeneous catalytic oxidation of carbon monoxide over platinum at atmospheric pressure under oscillatory conditions. Experiments are conducted in a continuous flow reactor, and the reaction rate is monitored using both infrared imaging and thermocouples. The catalysts are in the form of platinum annular thin films on washer-shaped quartz substrates, and they provide highly repeatable oscillatory behavior. Oscillations are typically spatially synchronized with the entire catalyst ``flashing'' on and off uniformly. Spatial coupling is investigated by introducing various barriers which split the annular ring in half. Infrared images show that coupling through the gas phase dominates coupling via the diffusion of CO on the surface or heat diffusion through the substrate. The introduction of a localized heat perturbation to the catalyst surface does not induce a transition in the reaction rate. Thus, it is likely that the primary mode of communication is through the gas-phase diffusion of reactants.

Green catalysis by nanoparticulate catalysts developed for flow processing? case study of glucose hydrogenation

NARCIS (Netherlands)

Gericke, D.; Ott-Reinhardt, D.; Matveeva, V.; Sulman, E.M.; Aho, A.; Murzin, D.Y.; Roggan, S.; Danilova, L.; Hessel, V.; Löb, P.; Kralisch, D.

2015-01-01

Heterogeneous catalysis, flow chemistry, continuous processing, green solvents, catalyst immobilization and recycling are some of the most relevant, emerging key technologies to achieve green synthesis. However, a quantification of potential effects on a case to case level is required to provide a

Theoretical Studies in Heterogenous Catalysis: Towards a Rational Design of Novel Catalysts for Hydrodesulfurization and Hydrogen Production

Energy Technology Data Exchange (ETDEWEB)

Rodriguez,J.A.; Liu, P.

2008-10-01

Traditionally, knowledge in heterogeneous catalysis has come through empirical research. Nowadays, there is a clear interest to change this since millions of dollars in products are generated every year in the chemical and petrochemical industries through catalytic processes. To obtain a fundamental knowledge of the factors that determine the activity of heterogeneous catalysts is a challenge for modern science since many of these systems are very complex in nature. In principle, when a molecule adsorbs on the surface of a heterogeneous catalyst, it can interact with a large number of bonding sites. It is known that the chemical properties of these bonding sites depend strongly on the chemical environment around them. Thus, there can be big variations in chemical reactivity when going from one region to another in the surface of a heterogeneous catalyst. A main objective is to understand how the structural and electronic properties of a surface affect the energetics for adsorption processes and the paths for dissociation and chemical reactions. In recent years, advances in instrumentation and experimental procedures have allowed a large series of detailed works on the surface chemistry of heterogeneous catalysts. In many cases, these experimental studies have shown interesting and unique phenomena. Theory is needed to unravel the basic interactions behind these phenomena and to provide a general framework for the interpretation of experimental results. Ideally, theoretical calculations based on density-functional theory have evolved to the point that one should be able to predict patterns in the activity of catalytic surfaces. As in the case of experimental techniques, no single theoretical approach is able to address the large diversity of phenomena occurring on a catalyst. Catalytic surfaces are usually modeled using either a finite cluster or a two-dimensionally periodic slab. Many articles have been published comparing the results of these two approaches. An

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...

Zeolites as supports for transition-metal complexes

Energy Technology Data Exchange (ETDEWEB)

Le Van Mao, R

1979-01-01

The unique structural characteristics of the zeolites, including the presence of molecular-size cages and channels and of an internal electrostatic field, make them promising as supports for converting homogeneous to heterogeneous catalysts. The acidic sites on the zeolites may also contribute to catalysis of reactions, such as hydrocracking; may stabilize metal complexes in a highly disperse state; and may improve activity or selectivity. Recent studies on the synthesis of new types of zeolite-supported complexes of transition metals (TM), such as Co, Cu, Ag, Fe, Mo, Ru, Rh, Re, and Os, suggest the feasibility of the direct introduction of some TM complexes into the zeolitic cages during zeolite synthesis, especially during the crystallization phase. This method may considerably reduce the structural limitations associated with the incorporation of TM complexes into zeolites by conventional methods.

Memory characteristics of an MOS capacitor structure with double-layer semiconductor and metal heterogeneous nanocrystals

International Nuclear Information System (INIS)

Ni Henan; Wu Liangcai; Song Zhitang; Hui Chun

2009-01-01

An MOS (metal oxide semiconductor) capacitor structure with double-layer heterogeneous nanocrystals consisting of semiconductor and metal embedded in a gate oxide for nonvolatile memory applications has been fabricated and characterized. By combining vacuum electron-beam co-evaporated Si nanocrystals and self-assembled Ni nanocrystals in a SiO 2 matrix, an MOS capacitor with double-layer heterogeneous nanocrystals can have larger charge storage capacity and improved retention characteristics compared to one with single-layer nanocrystals. The upper metal nanocrystals as an additional charge trap layer enable the direct tunneling mechanism to enhance the flat voltage shift and prolong the retention time. (semiconductor devices)

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)

The performance of 3500 MWth homogeneous and heterogeneous metal fueled core designs

International Nuclear Information System (INIS)

Turski, R.; Yang, Shi-tien.

1987-11-01

Performance parameters are calculated for a representative 3500 MWth homogeneous and a heterogeneous metal fueled reactor design. The equilibrium cycle neutronic characteristics, safety coefficients, control system requirements, and control rod worths are evaluated. The thermal-hydraulic characteristics for both configurations are also compared. The heavy metal fuel loading requirements and neutronic performance characteristics are also evaluated for the uranium startup option. 14 refs., 14 figs., 20 tabs

Utilisation of CO2, fixation of nitrogen and exhaust gas cleaning in electric discharge with electrode catalysis

International Nuclear Information System (INIS)

Marcela, M.; Imrich, M.; Mario, J.

2001-01-01

The method reported here provides a contribution to CO 2 utilisation, nitrogen fixation and combustion exhaust cleaning using synergetic effect of electric discharge with heterogeneous catalysis on electrodes. The efficiency of CO 2 removal is about 40-65%. The process of CO 2 removal is always accompanied by NO x , VOC, SX and other component removal and is connected with O 2 formation. The final product of process is powder with fractal microstructure, low specific weight, water insoluble suitable for use as nitrogen containing fertilizer. The main component (95%) of solid product is amorphous condensate of amino acids with about 5% of metal organic compound with catalytic properties. The condensate has character of statistical proteinoid. Its creation seems to play important role during formation of life in pre-biotic Earth

Graphene: a promising two-dimensional support for heterogeneous catalysts

Directory of Open Access Journals (Sweden)

Xiaobin eFan

2015-01-01

Full Text Available Graphene has many advantages that make it an attractive two-dimensional (2D support for heterogeneous catalysts. It not only allows the high loading of targeted catalytic species, but also facilitates the mass transfer during the reaction processes. These advantages, along with its unique physical and chemical properties, endow graphene great potential as catalyst support in heterogeneous catalysis.

Environmental dynamics of metal oxide nanoparticles in heterogeneous systems: A review

International Nuclear Information System (INIS)

Joo, Sung Hee; Zhao, Dongye

2017-01-01

Highlights: • Influence of contaminants on the mobility of metal oxide nanoparticles (MNPs). • Synergistic effects of MNPs in the presence of contaminants. • Effect of environmental factors on the transformed MNPs. • Research direction on the toxicity modeling assessment of heterogeneous systems. - Abstract: Metal oxide nanoparticles (MNPs) have been used for many purposes including water treatment, health, cosmetics, electronics, food packaging, and even food products. As their applications continue to expand, concerns have been mounting about the environmental fate and potential health risks of the nanoparticles in the environment. Based on the latest information, this review provides an overview of the factors that affect the fate, transformation and toxicity of MNPs. Emphasis is placed on the effects of various aquatic contaminants under various environmental conditions on the transformation of metal oxides and their transport kinetics – both in homogeneous and heterogeneous systems – and the effects of contaminants on the toxicity of MNPs. The presence of existing contaminants decreases bioavailability through hetero-aggregation, sorption, and/or complexation upon an interaction with MNPs. Contaminants also influence the fate and transport of MNPs and exhibit their synergistic toxic effects that contribute to the extent of the toxicity. This review will help regulators, engineers, and scientists in this field to understand the latest development on MNPs, their interactions with aquatic contaminants as well as the environmental dynamics of their fate and transformation. The knowledge gap and future research needs are also identified, and the challenges in assessing the environmental fate and transport of nanoparticles in heterogeneous systems are discussed.

Environmental dynamics of metal oxide nanoparticles in heterogeneous systems: A review

Energy Technology Data Exchange (ETDEWEB)

Joo, Sung Hee, E-mail: s.joo1@miami.edu [Department of Civil, Architectural, and Environmental Engineering, University of Miami, 1251 Memorial Dr. McArthur Engineering Building, Coral Gables, FL 33146-0630 (United States); Zhao, Dongye [Department of Civil and Environmental Engineering, 238 Harbert Engineering Center, Auburn University, Auburn, AL 36849 (United States)

2017-01-15

Highlights: • Influence of contaminants on the mobility of metal oxide nanoparticles (MNPs). • Synergistic effects of MNPs in the presence of contaminants. • Effect of environmental factors on the transformed MNPs. • Research direction on the toxicity modeling assessment of heterogeneous systems. - Abstract: Metal oxide nanoparticles (MNPs) have been used for many purposes including water treatment, health, cosmetics, electronics, food packaging, and even food products. As their applications continue to expand, concerns have been mounting about the environmental fate and potential health risks of the nanoparticles in the environment. Based on the latest information, this review provides an overview of the factors that affect the fate, transformation and toxicity of MNPs. Emphasis is placed on the effects of various aquatic contaminants under various environmental conditions on the transformation of metal oxides and their transport kinetics – both in homogeneous and heterogeneous systems – and the effects of contaminants on the toxicity of MNPs. The presence of existing contaminants decreases bioavailability through hetero-aggregation, sorption, and/or complexation upon an interaction with MNPs. Contaminants also influence the fate and transport of MNPs and exhibit their synergistic toxic effects that contribute to the extent of the toxicity. This review will help regulators, engineers, and scientists in this field to understand the latest development on MNPs, their interactions with aquatic contaminants as well as the environmental dynamics of their fate and transformation. The knowledge gap and future research needs are also identified, and the challenges in assessing the environmental fate and transport of nanoparticles in heterogeneous systems are discussed.

The 'Invisible' Metal Particles in Catalysis

NARCIS (Netherlands)

Koningsberger, D.C.; Diaz-Moreno, S.; Muñoz-Paez, A.

1997-01-01

An easy, reliable and straightforward method to determine the sizes of small metal particles in supported metal catalyst which are invisible for most techniques (chemisorption, XRD, HRTEM) is presented. The technique we consider more appropriate is EXAFS, because it detects metal metal bonds even

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

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

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).

Metal Fluorides, Metal Chlorides and Halogenated Metal Oxides as Lewis Acidic Heterogeneous Catalysts. Providing Some Context for Nanostructured Metal Fluorides.

Science.gov (United States)

Lennon, David; Winfield, John M

2017-01-28

Aspects of the chemistry of selected metal fluorides, which are pertinent to their real or potential use as Lewis acidic, heterogeneous catalysts, are reviewed. Particular attention is paid to β-aluminum trifluoride, aluminum chlorofluoride and aluminas γ and η, whose surfaces become partially fluorinated or chlorinated, through pre-treatment with halogenating reagents or during a catalytic reaction. In these cases, direct comparisons with nanostructured metal fluorides are possible. In the second part of the review, attention is directed to iron(III) and copper(II) metal chlorides, whose Lewis acidity and potential redox function have had important catalytic implications in large-scale chlorohydrocarbons chemistry. Recent work, which highlights the complexity of reactions that can occur in the presence of supported copper(II) chloride as an oxychlorination catalyst, is featured. Although direct comparisons with nanostructured fluorides are not currently possible, the work could be relevant to possible future catalytic developments in nanostructured materials.

Intraparticulate Metal Speciation Analysis of Soft Complexing Nanoparticles. The Intrinsic Chemical Heterogeneity of Metal-Humic Acid Complexes

DEFF Research Database (Denmark)

Town, R. M.; van Leeuwen, Herman P.

2016-01-01

ion condensation potential for higher valency counterions within the intraparticulate double layer zone of the soft NP. The approach offers new insights into the intrinsic heterogeneity of the HA. complexes, as revealed by the intraparticulate speciation as a function of the true degree of inner......-sphere complexation, theta(M). The ensuing intrinsic heterogeneity parameters, Gamma, for CdHA and CuHA complexes are in very good agreement with those obtained from dynamic electrochemical stripping chronopotentiometric measurements. The overall intraparticulate metal ion speciation is found to depend on theta...

Surface-Enhanced Raman Spectroscopy for Heterogeneous Catalysis Research

NARCIS (Netherlands)

Harvey, C.E.

2013-01-01

Raman spectroscopy is valuable characterization technique for the chemical analysis of heterogeneous catalysts, both under ex-situ and in-situ conditions. The potential for Raman to shine light on the chemical bonds present in a sample makes the method highly desirable for detailed catalyst

Dynamical, structural and chemical heterogeneities in a binary metallic glass-forming liquid

Science.gov (United States)

Puosi, F.; Jakse, N.; Pasturel, A.

2018-04-01

As it approaches the glass transition, particle motion in liquids becomes highly heterogeneous and regions with virtually no mobility coexist with liquid-like domains. This complex dynamic is believed to be responsible for different phenomena including non-exponential relaxation and the breakdown of the Stokes-Einstein relation. Understanding the relationships between dynamical heterogeneities and local structure in metallic liquids and glasses is a major scientific challenge. Here we use classical molecular dynamics simulations to study the atomic dynamics and microscopic structure of Cu50Zr50 alloy in the supercooling regime. Dynamical heterogeneities are identified via an isoconfigurational analysis. We demonstrate the transition from isolated to clustering low mobility with decreasing temperature. These slow clusters, whose sizes grow upon cooling, are also associated with concentration fluctuations, characterized by a Zr-enriched phase, with a composition CuZr2 . In addition, a structural analysis of slow clusters based on Voronoi tessellation evidences an increase with respect of the bulk system of the fraction of Cu atoms having a local icosahedral order. These results are in agreement with the consolidated scenario of the relevant role played by icosahedral order in the dynamic slowing-down in supercooled metal alloys.

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...

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

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)

NMR Computational Studies of Solid Acidity/Fundamental Studies of Catalysis by Solid Acids

Energy Technology Data Exchange (ETDEWEB)

James F. Haw

2008-06-28

This project focused on catalysis by zeolites and the synergy of spectroscopic characterization and theoretical modeling. In collaboration with the Waroquier group in Belgium we used state-of-the-art quantum chemical simulations on a supramolecular model of both the HZSM-5 zeolite and the co-catalytic hydrocarbon pool species and calculated a full catalytic cycle (including all rate constants) for methanol-to-olefin (MTO) catalysis involving a hydrocarbon pool species. This work not only represents the most robust computational analysis of a successful MTO route to date, but it also succeeds in tying together the many experimental clues. That work was featured on the cover of Angewandte Chemie. More recently we elucidated several unsuspected roles for formaldehyde in methanol to olefin catalysis. Formaldehyde proves to be a key species responsible for both the growth of the catalytically active hydrocarbon pool and its inevitable aging into deactivated polycyclic aromatic species. The apparent inevitability of formaldehyde formation at high temperatures, in particular in contact with active metal or metal oxide surfaces, may put some fundamental limitations on the economic potential of conversion of methanol to olefins.

Structural basis for catalysis at the membrane-water interface.

Science.gov (United States)

Dufrisne, Meagan Belcher; Petrou, Vasileios I; Clarke, Oliver B; Mancia, Filippo

2017-11-01

The membrane-water interface forms a uniquely heterogeneous and geometrically constrained environment for enzymatic catalysis. Integral membrane enzymes sample three environments - the uniformly hydrophobic interior of the membrane, the aqueous extramembrane region, and the fuzzy, amphipathic interfacial region formed by the tightly packed headgroups of the components of the lipid bilayer. Depending on the nature of the substrates and the location of the site of chemical modification, catalysis may occur in each of these environments. The availability of structural information for alpha-helical enzyme families from each of these classes, as well as several beta-barrel enzymes from the bacterial outer membrane, has allowed us to review here the different ways in which each enzyme fold has adapted to the nature of the substrates, products, and the unique environment of the membrane. Our focus here is on enzymes that process lipidic substrates. This article is part of a Special Issue entitled: Bacterial Lipids edited by Russell E. Bishop. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

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

Surface/structure functionalization of copper-based catalysts by metal-support and/or metal-metal interactions

Science.gov (United States)

Konsolakis, Michalis; Ioakeimidis, Zisis

2014-11-01

Cu-based catalysts have recently attracted great attention both in catalysis and electro-catalysis fields due to their excellent catalytic performance and low cost. Given that their performance is determined, to a great extent, by Cu sites local environment, considerable efforts have been devoted on the strategic modifications of the electronic and structural properties of Cu sites. In this regard, the feasibility of tuning the local structure of Cu entities by means of metal-support or metal-metal interactions is investigated. More specifically, the physicochemical properties of Cu entities are modified by employing: (i) different oxides (CeO2, La2O3, Sm2O3), or (ii) ceria-based mixed oxides (Ce1-xSmxOδ) as supporting carriers, and (iii) a second metal (Cobalt) adjacent to Cu (bimetallic Cu-Co/CeO2). A characterization study, involving BET, XRD, TPR, and XPS, reveal that significant modifications on structural, redox and electronic properties of Cu sites can be induced by adopting either different oxide carriers or bimetallic complexes. Fundamental insights into the tuning of Cu local environment by metal-support or metal-metal interactions are provided, paving the way for real-life industrial applications.

Treatment of decontamination liquid waste of nuclear power plant components by heterogeneous photo catalysis with a continuous recirculation equipment

International Nuclear Information System (INIS)

Litter, Marta I.; La Gamma, Ana M.; Chocron, Mauricio; Blesa, Miguel A.; Repetto, Pablo

1999-01-01

It has been designed a bench scale, recirculation device, for testing the degradation of solutions of ethylendiamine tetraacetic acid (EDTA) by heterogeneous photo catalysis under irradiation with UV and titanium dioxide (TiO 2 ). Solutions of EDTA have been employed at concentrations and pH values similar to those used when a decontamination of nuclear power plant equipment is carried out. The circuit is composed of a photo reactor, a heat exchanger, a reservoir tank and a peristaltic pump. In the present paper, the results of the experiments of photo catalytic degradation of aqueous suspensions of TiO 2 (Degussa P-25) 1 g/L with EDTA (10 g/L) at pH 3.7 and 25 degree C and two irradiation wavelengths (366 and 254 nm) have been presented. At 366 nm the full degradation of EDTA has occurred in 10 hours. The 95% degradation of total organic carbon (TOC) has been achieved after 39 hours of irradiation. The irradiation at 254 nm in the same conditions has been much less effective (EDTA and TOC reduction of approximately 1%), due to a screening effect produced by the semiconductor. (author)

Understanding Atom Probe Tomography of Oxide-Supported Metal Nanoparticles by Correlation with Atomic-Resolution Electron Microscopy and Field Evaporation Simulation.

Science.gov (United States)

Devaraj, Arun; Colby, Robert; Vurpillot, François; Thevuthasan, Suntharampillai

2014-04-17

Oxide-supported metal nanoparticles are widely used in heterogeneous catalysis. The increasingly detailed design of such catalysts necessitates three-dimensional characterization with high spatial resolution and elemental selectivity. Laser-assisted atom probe tomography (APT) is uniquely suited to the task but faces challenges with the evaporation of metal/insulator systems. Correlation of APT with aberration-corrected scanning transmission electron microscopy (STEM), for Au nanoparticles embedded in MgO, reveals preferential evaporation of the MgO and an inaccurate assessment of nanoparticle composition. Finite element field evaporation modeling is used to illustrate the evolution of the evaporation front. Nanoparticle composition is most accurately predicted when the MgO is treated as having a locally variable evaporation field, indicating the importance of considering laser-oxide interactions and the evaporation of various molecular oxide ions. These results demonstrate the viability of APT for analysis of oxide-supported metal nanoparticles, highlighting the need for developing a theoretical framework for the evaporation of heterogeneous materials.

Prediction of molecular separation of polar-apolar mixtures on heterogeneous metal-organic frameworks: HKUST-1.

Science.gov (United States)

Van Assche, Tom R C; Duerinck, Tim; Van der Perre, Stijn; Baron, Gino V; Denayer, Joeri F M

2014-07-08

Due to the combination of metal ions and organic linkers and the presence of different types of cages and channels, metal-organic frameworks often possess a large structural and chemical heterogeneity, complicating their adsorption behavior, especially for polar-apolar adsorbate mixtures. By allocating isotherms to individual subunits in the structure, the ideal adsorbed solution theory (IAST) can be adjusted to cope with this heterogeneity. The binary adsorption of methanol and n-hexane on HKUST-1 is analyzed using this segregated IAST (SIAST) approach and offers a significant improvement over the standard IAST model predictions. It identifies the various HKUST-1 cages to have a pronounced polar or apolar adsorptive behavior.

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.

Selective Oxidations using Nanostructured Heterogeneous Catalysts

DEFF Research Database (Denmark)

Mielby, Jerrik Jørgen

and because they produce H2O as the only by-product. Chapter 1 gives a short introduction to basic concepts in heterogeneous catalysis and green chemistry. Furthermore, the chapter gives an overview of the most important strategies to synthesise functional nanostructured materials and highlights how detailed......The aim of this thesis is to investigate and develop new efficient methods to oxidise alcohols and amines using heterogeneous catalysts and either O2 or H2O2 as oxidants. From an economic and environmental point of view, these oxidants are ideal, because they are cheap and readily available...... understanding of size, shape and structure can help in the development of new and more efficient heterogeneous catalysts. The chapter is not intended to give a complete survey, but rather to introduce some of the recent developments in the synthesis of nanostructured heterogeneous catalysts. Finally...

The recent development of efficient Earth-abundant transition-metal nanocatalysts.

Science.gov (United States)

Wang, Dong; Astruc, Didier

2017-02-06

Whereas noble metal compounds have long been central in catalysis, Earth-abundant metal-based catalysts have in the same time remained undeveloped. Yet the efficacy of Earth-abundant metal catalysts was already shown at the very beginning of the 20th century with the Fe-catalyzed Haber-Bosch process of ammonia synthesis and later in the Fischer-Tropsch reaction. Nanoscience has revolutionized the world of catalysis since it was observed that very small Au nanoparticles (NPs) and other noble metal NPs are extraordinarily efficient. Therefore the development of Earth-abundant metals NPs is more recent, but it has appeared necessary due to their "greenness". This review highlights catalysis by NPs of Earth-abundant transition metals that include Mn, Fe, Co, Ni, Cu, early transition metals (Ti, V, Cr, Zr, Nb and W) and their nanocomposites with emphasis on basic principles and literature reported during the last 5 years. A very large spectrum of catalytic reactions has been successfully disclosed, and catalysis has been examined for each metal starting with zero-valent metal NPs followed by oxides and other nanocomposites. The last section highlights the catalytic activities of bi- and trimetallic NPs. Indeed this later family is very promising and simultaneously benefits from increased stability, efficiency and selectivity, compared to monometallic NPs, due to synergistic substrate activation.

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.

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.

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)

The Electronic Structure Effect in Heterogeneous Catalysis

DEFF Research Database (Denmark)

Nilsson, A.; Pettersson, L. G. M.; Hammer, Bjørk

2005-01-01

Using a combination of density functional theory calculations and X-ray emission and absorption spectroscopy for nitrogen on Cu and Ni surfaces, a detailed picture is given of the chemisorption bond. It is suggested that the adsorption bond strength and hence the activity of transition metal surf...

Applications of neutron scattering to heterogeneous catalysis

International Nuclear Information System (INIS)

Parker, Stewart F; Lennon, David

2016-01-01

Historically, most studies of heterogeneous catalysts that have used neutron vibrational spectroscopy have employed indirect geometry instruments with a low (<40 cm -1 ) final energy. In this paper we examine the reasons why this has been the case and highlight the advantages and disadvantages of this approach. We then show how some of these may be overcome by the use of direct geometry spectrometers. We illustrate the use of direct geometry spectrometers with examples from reforming of methane to synthesis gas (CO + H 2 ) over Ni/Al 2 O 3 catalysts and an operando study of CO oxidation. We conclude with a proposal for a unique instrument that combines both indirect and direct geometry spectrometers. (paper)

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

Heterogeneous Organo-Catalysis: Sustainable Pathways to Furanics from Biomass

Science.gov (United States)

Glucose and fructose are among the most abundant plant-derived materials1 and have been converted into useful building units often used in the drug discovery and polymer architecture.2 Unfortunately, most of these conversions require mineral acids and complex heterogeneous cataly...

Stabilizing ultrasmall Au clusters for enhanced photoredox catalysis.

Science.gov (United States)

Weng, Bo; Lu, Kang-Qiang; Tang, Zichao; Chen, Hao Ming; Xu, Yi-Jun

2018-04-18

Recently, loading ligand-protected gold (Au) clusters as visible light photosensitizers onto various supports for photoredox catalysis has attracted considerable attention. However, the efficient control of long-term photostability of Au clusters on the metal-support interface remains challenging. Herein, we report a simple and efficient method for enhancing the photostability of glutathione-protected Au clusters (Au GSH clusters) loaded on the surface of SiO 2 sphere by utilizing multifunctional branched poly-ethylenimine (BPEI) as a surface charge modifying, reducing and stabilizing agent. The sequential coating of thickness controlled TiO 2 shells can further significantly improve the photocatalytic efficiency, while such structurally designed core-shell SiO 2 -Au GSH clusters-BPEI@TiO 2 composites maintain high photostability during longtime light illumination conditions. This joint strategy via interfacial modification and composition engineering provides a facile guideline for stabilizing ultrasmall Au clusters and rational design of Au clusters-based composites with improved activity toward targeting applications in photoredox catalysis.

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

Population-level consequences of spatially heterogeneous exposure to heavy metals in soil: An individual-based model of springtails

DEFF Research Database (Denmark)

Meli, Mattia; Auclerc, Apolline; Palmqvist, Annemette

2013-01-01

Contamination of soil with toxic heavy metals poses a major threat to the environment and human health. Anthropogenic sources include smelting of ores, municipal wastes, fertilizers, and pesticides. In assessing soil quality and the environmental and ecological risk of contamination with heavy...... metals, often homogeneous contamination of the soil is assumed. However, soils are very heterogeneous environments. Consequently, both contamination and the response of soil organisms can be assumed to be heterogeneous. This might have consequences for the exposure of soil organisms...

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.

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

Understanding the Enhanced Catalytic Performance of Ultrafine Transition Metal Nanoparticles–Graphene Composites

KAUST Repository

Liu, Xin

2015-08-11

Catalysis, as the key to minimize the energy requirement and environmental impact of today\\'s chemical industry, plays a vital role in many fields directly related to our daily life and economy, including energy generation, environment control, manufacture of chemicals, medicine synthesis, etc. Rational design and fabrication of highly efficient catalysts have become the ultimate goal of today\\'s catalysis research. For the purpose of handling and product separation, heterogeneous catalysts are highly preferred for industrial applications and a large part of which are the composites of transition metal nanoparticles (TMNPs). With the fast development of nanoscience and nanotechnology and assisted with theoretical investigations, basic understanding on tailoring the electronic structure of these nanocomposites has been gained, mainly by precise control of the composition, morphology, interfacial structure and electronic states. With the rise of graphene, chemical routes to prepare graphene were developed and various graphene-based composites were fabricated. Transition metal nanoparticles-reduced graphene oxide (TMNPs–rGO) composites have attracted considerable attention, because of their intriguing catalytic performance which have been extensively explored for energy- and environment-related applications to date. This review summarizes our recent experimental and theoretical efforts on understanding the superior catalytic performance of subnanosized TMNPs–rGO composites.

Roles of the active site residues and metal cofactors in noncanonical base-pairing during catalysis by human DNA polymerase iota.

Science.gov (United States)

Makarova, Alena V; Ignatov, Artem; Miropolskaya, Nataliya; Kulbachinskiy, Andrey

2014-10-01

Human DNA polymerase iota (Pol ι) is a Y-family polymerase that can bypass various DNA lesions but possesses very low fidelity of DNA synthesis in vitro. Structural analysis of Pol ι revealed a narrow active site that promotes noncanonical base-pairing during catalysis. To better understand the structure-function relationships in the active site of Pol ι we investigated substitutions of individual amino acid residues in its fingers domain that contact either the templating or the incoming nucleotide. Two of the substitutions, Y39A and Q59A, significantly decreased the catalytic activity but improved the fidelity of Pol ι. Surprisingly, in the presence of Mn(2+) ions, the wild-type and mutant Pol ι variants efficiently incorporated nucleotides opposite template purines containing modifications that disrupted either Hoogsteen or Watson-Crick base-pairing, suggesting that Pol ι may use various types of interactions during nucleotide addition. In contrast, in Mg(2+) reactions, wild-type Pol ι was dependent on Hoogsteen base-pairing, the Y39A mutant was essentially inactive, and the Q59A mutant promoted Watson-Crick interactions with template purines. The results suggest that Pol ι utilizes distinct mechanisms of nucleotide incorporation depending on the metal cofactor and reveal important roles of specific residues from the fingers domain in base-pairing and catalysis. Copyright © 2014 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.

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.

Catalytic Ionic-Liquid Membranes: The Convergence of Ionic-Liquid Catalysis and Ionic-Liquid Membrane Separation Technologies.

Czech Academy of Sciences Publication Activity Database

Izák, Pavel; Bobbink, F.D.; Hulla, M.; Klepic, M.; Friess, K.; Hovorka, Š.; Dyson, P.J.

2018-01-01

Roč. 83, č. 1 (2018), s. 7-18 ISSN 2192-6506 R&D Projects: GA ČR(CZ) GA17-00089S; GA ČR GA17-05421S Institutional support: RVO:67985858 Keywords : heterogeneous catalysis * ionic liquids * membranes Subject RIV: CI - Industrial Chemistry, Chemical Engineering OBOR OECD: Chemical process engineering Impact factor: 2.797, year: 2016

Surface science and model catalysis with ionic liquid-modified materials.

Science.gov (United States)

Steinrück, H-P; Libuda, J; Wasserscheid, P; Cremer, T; Kolbeck, C; Laurin, M; Maier, F; Sobota, M; Schulz, P S; Stark, M

2011-06-17

Materials making use of thin ionic liquid (IL) films as support-modifying functional layer open up a variety of new possibilities in heterogeneous catalysis, which range from the tailoring of gas-surface interactions to the immobilization of molecularly defined reactive sites. The present report reviews recent progress towards an understanding of "supported ionic liquid phase (SILP)" and "solid catalysts with ionic liquid layer (SCILL)" materials at the microscopic level, using a surface science and model catalysis type of approach. Thin film IL systems can be prepared not only ex-situ, but also in-situ under ultrahigh vacuum (UHV) conditions using atomically well-defined surfaces as substrates, for example by physical vapor deposition (PVD). Due to their low vapor pressure, these systems can be studied in UHV using the full spectrum of surface science techniques. We discuss general strategies and considerations of this approach and exemplify the information available from complementary methods, specifically photoelectron spectroscopy and surface vibrational spectroscopy. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Lignin Valorization using Heterogenous Catalytic Oxidation

DEFF Research Database (Denmark)

Melián Rodríguez, Mayra; Shunmugavel, Saravanamurugan; Kegnæs, Søren

The research interests in biomass conversion to fuels and chemicals has increased significantly in the last decade in view of current problems such as global warming, high oil prices, food crisis and other geopolitical scenarios. Many different reactions and processes to convert biomass into high...... of the reaction conditions 4. Here, we therefore present an overview of the recent research about conversion of some lignin model compounds using heterogeneous catalysis in oxidation reactions....

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

π-face donation from the aromatic N-substituent of N-heterocyclic carbene ligands to metal and its role in catalysis

KAUST Repository

Credendino, Raffaele

2012-05-16

In this work, we calculate the redox potential in a series of Ir and Ru complexes bearing a N-heterocyclic carbene (NHC) ligand presenting different Y groups in the para position of the aromatic N-substituent. The calculated redox potentials excellently correlate with the experimental ΔE 1/2 potentials, offering a handle to rationalize the experimental findings. Analysis of the HOMO of the complexes before oxidation suggests that electron-donating Y groups destabilize the metal centered HOMO. Energy decomposition of the metal-NHC interaction indicates that electron-donating Y groups reinforce this interaction in the oxidized complexes. Analysis of the electron density in the reduced and oxidized states of representative complexes indicates a clear donation from the C ipso of the N-substituents to an empty d orbital on the metal. In case of the Ru complexes, this mechanism involves the Ru-alkylidene moiety. All of these results suggest that electron-donating Y groups render the aromatic N-substituent able to donate more density to electron-deficient metals through the C ipso atom. This conclusion suggests that electron-donating Y groups could stabilize higher oxidation states during catalysis. To test this hypothesis, we investigated the effect of differently donating Y groups in model reactions of Ru-catalyzed olefin metathesis and Pd-catalyzed C-C cross-coupling. Consistent with the experimental results, calculations indicate an easier reaction pathway if the N-substituent of the NHC ligand presents an electron-donating Y group. © 2012 American Chemical Society.

Hydrogen and methane synthesis through radiation catalysis. Final report

International Nuclear Information System (INIS)

DuBow, J.

1980-09-01

The goal of this research was to evaluate the potential for using reactor wastes to synthesize useful products in quasi-photochemical configuration. It was found that semiconductor oxides act as heterogenous catalysts for the formation of H 2 in aqueous media under 60 Co irradiation. The principle of a gamma-ray solar cell was demonstrated experimentally. Experiments with ultraviolet irradiated TiO 2 and ZnO grains demonstrated that both H 2 and H 2 O 2 were formed, in contrast to the results of work by previous authors. These results were rationalized by energy band diagram representations and by applying principles of semiconductor photoelectrochemistry. The concept of gamma-ray assisted desulfurization of coal through radiological degradation and heterogenous catalysis was experimentally demonstrated. The proof-of-concept experiments in the present study provide the basis for further fundamental and applied investigations, particularly in a potentially efficient system with a fresh source and 1.5 m path length

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

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...

Transition Metal Complexes and Catalysis

Indian Academy of Sciences (India)

approaches towards the study of bonding in transition metal complexes. Despite .... industrial scale reactions for the production of organic compounds using transition ..... It has found several applications as an engineering thermoplastic. .... and processes of interest to the company, that is, applied research. It is this very ...

Incorporation of metals (Pt-Ni-Ru) in the zeolite ZSM-5 through ion exchange competitive: synthesis and characterization

International Nuclear Information System (INIS)

Barbosa, A.S.; Rodrigues, M.G.F.

2012-01-01

Zeolites are very important materials due to their high specific surface area. Moreover, they are suitable for use as catalyst support. Noble metals supported on zeolites have been widely used as catalysts in the petrochemical industry. This paper was prepared and characterized, a powder aiming its use in heterogeneous catalysis. Support was used as ZSM-5 and the method of incorporation of the metals (Ru-PtNi) was competitive ion exchange. The materials (ZSM-5 and Pt-Ni-Ru/ZSM-5) were characterized by spectrophotometry Energy Dispersive X-ray (EDX), X-Ray Diffraction (XRD) and nitrogen physisorption (BET method). Based on the results of X-ray diffraction, it is possible to demonstrate the preservation of the structure of zeolite ZSM-5 after the competitive ion Exchange with metals (Ru-Pt-Ni) and calcination. The dispersion of metals on ZSM-5 did not change the textural characteristics of the zeolite. (author)

Nanostructured metal-polyaniline composites

Science.gov (United States)

Wang, Hsing-Lin; Li, Wenguang; Bailey, James A.; Gao, Yuan

2010-08-31

Metal-polyaniline (PANI) composites are provided together with a process of preparing such composites by an electrodeless process. The metal of the composite can have nanoscale structural features and the composites can be used in applications such as catalysis for hydrogenation reactions and for analytical detection methods employing SERS.

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

Green chemistry by nano-catalysis

KAUST Repository

Polshettiwar, Vivek; Varma, Rajender S.

2010-01-01

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

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

Porous metallosilicates for heterogeneous, liquid-phase catalysis: perspectives and pertaining challenges

Science.gov (United States)

Hammond, Ceri; Padovan, Daniele; Tarantino, Giulia

2018-02-01

Porous silicates containing dilute amounts of tri-, tetra- and penta-valent metal sites, such as TS-1, Sn-β and Fe-ZSM-5, have recently emerged as state of the art catalysts for a variety of sustainable chemical transformations. In contrast with their aluminosilicate cousins, which are widely employed throughout the refinery industry for gas-phase catalytic transformations, such metallosilicates have exhibited unprecedented levels of performance for a variety of liquid-phase catalytic processes, including the conversion of biomass to chemicals, and sustainable oxidation technologies with H2O2. However, despite their unique levels of performance for these new types of chemical transformations, increased utilization of these promising materials is complicated by several factors. For example, their utilization in a liquid, and often polar, medium hinders process intensification (scale-up, catalyst deactivation). Moreover, such materials do not generally exhibit the active-site homogeneity of conventional aluminosilicates, and they typically possess a wide variety of active-site ensembles, only some of which may be directly involved in the catalytic chemistry of interest. Consequently, mechanistic understanding of these catalysts remains relatively low, and competitive reactions are commonly observed. Accordingly, unified approaches towards developing more active, selective and stable porous metallosilicates have not yet been achieved. Drawing on some of the most recent literature in the field, the purpose of this mini review is both to highlight the breakthroughs made with regard to the use of porous metallosilicates as heterogeneous catalysts for liquid-phase processing, and to highlight the pertaining challenges that we, and others, aim to overcome during the forthcoming years.

Decoration of Multi-walled Carbon Nanotubes by Metal ...

African Journals Online (AJOL)

NICO

tures inside the nanotubes to increase the available surface for catalysis6 or in ... most common method to decorate CNTs by metal nanoparticles and metal oxides due .... 2.6 Characterization of Carbon Nanotubes, Metal Nano- particles and ...

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.

Role of bonding mechanisms during transfer hydrogenation reaction on heterogeneous catalysts of platinum nanoparticles supported on zinc oxide nanorods

Science.gov (United States)

Al-Alawi, Reem A.; Laxman, Karthik; Dastgir, Sarim; Dutta, Joydeep

2016-07-01

For supported heterogeneous catalysis, the interface between a metal nanoparticle and the support plays an important role. In this work the dependency of the catalytic efficiency on the bonding chemistry of platinum nanoparticles supported on zinc oxide (ZnO) nanorods is studied. Platinum nanoparticles were deposited on ZnO nanorods (ZnO NR) using thermal and photochemical processes and the effects on the size, distribution, density and chemical state of the metal nanoparticles upon the catalytic activities are presented. The obtained results indicate that the bonding at Pt-ZnO interface depends on the deposition scheme which can be utilized to modulate the surface chemistry and thus the activity of the supported catalysts. Additionally, uniform distribution of metal on the catalyst support was observed to be more important than the loading density. It is also found that oxidized platinum Pt(IV) (platinum hydroxide) provided a more suitable surface for enhancing the transfer hydrogenation reaction of cyclohexanone with isopropanol compared to zero valent platinum. Photochemically synthesized ZnO supported nanocatalysts were efficient and potentially viable for upscaling to industrial applications.

Nanochemistry of metals

International Nuclear Information System (INIS)

Sergeev, Gleb B

2001-01-01

The results of studies on the nanochemistry of metals published in recent years are generalised. Primary attention is centred on the methods for the synthesis of nanoparticles and their chemical reactions. The means of stabilisation of nanoparticles which involve individual metals and incorporate atoms of several metals are considered as well as their physicochemical properties. Self-assembling processes of nanoparticles are described. The prospects of using metal nanoparticles in semiconductor devices, catalysis, biology and medicine are discussed. The bibliography includes 165 references.

Specific acid catalysis and Lewis acid catalysis of Diels–Alder reactions in aqueous media

NARCIS (Netherlands)

Mubofu, Egid B.; Engberts, Jan B.F.N.

2004-01-01

A comparative study of specific acid catalysis and Lewis acid catalysis of Diels–Alder reactions between dienophiles (1, 4 and 6) and cyclopentadiene (2) in water and mixed aqueous media is reported. The reactions were performed in water with copper(II) nitrate as the Lewis acid catalyst whereas

Specific acid catalysis and Lewis acid catalysis of Diels-Alder reactions in aqueous media

NARCIS (Netherlands)

Mubofu, E.B.; Engberts, J.B.F.N.

A comparative study of specific acid catalysis and Lewis acid catalysis of Diells-Alder reactions between dienophiles (1, 4 and 6) and cyclopentadiene (2) in water and mixed aqueous media is reported. The reactions were performed in water with copper(II) nitrate as the Lewis acid catalyst whereas

Nanomaterials derived from metal-organic frameworks

Science.gov (United States)

Dang, Song; Zhu, Qi-Long; Xu, Qiang

2018-01-01

The thermal transformation of metal-organic frameworks (MOFs) generates a variety of nanostructured materials, including carbon-based materials, metal oxides, metal chalcogenides, metal phosphides and metal carbides. These derivatives of MOFs have characteristics such as high surface areas, permanent porosities and controllable functionalities that enable their good performance in sensing, gas storage, catalysis and energy-related applications. Although progress has been made to tune the morphologies of MOF-derived structures at the nanometre scale, it remains crucial to further our knowledge of the relationship between morphology and performance. In this Review, we summarize the synthetic strategies and optimized methods that enable control over the size, morphology, composition and structure of the derived nanomaterials. In addition, we compare the performance of materials prepared by the MOF-templated strategy and other synthetic methods. Our aim is to reveal the relationship between the morphology and the physico-chemical properties of MOF-derived nanostructures to optimize their performance for applications such as sensing, catalysis, and energy storage and conversion.

Modeling and simulation of heterogeneous catalytic processes

CERN Document Server

Dixon, Anthony

2014-01-01

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

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

CERN Document Server

Busca, Guido

2014-01-01

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

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)

Creation of metal-independent hyperthermophilic L-arabinose isomerase by homologous recombination.

Science.gov (United States)

Hong, Young-Ho; Lee, Dong-Woo; Pyun, Yu-Ryang; Lee, Sung Haeng

2011-12-28

Hyperthermophilic L-arabinose isomerases (AIs) are useful in the commercial production of D-tagatose as a low-calorie bulk sweetener. Their catalysis and thermostability are highly dependent on metals, which is a major drawback in food applications. To study the role of metal ions in the thermostability and catalysis of hyperthermophilic AI, four enzyme chimeras were generated by PCR-based hybridization to replace the variable N- and C-terminal regions of hyperthermophilic Thermotoga maritima AI (TMAI) and thermophilic Geobacillus stearothermophilus AI (GSAI) with those of the homologous mesophilic Bacillus halodurans AI (BHAI). Unlike Mn(2+)-dependent TMAI, the GSAI- and TMAI-based hybrids with the 72 C-terminal residues of BHAI were not metal-dependent for catalytic activity. By contrast, the catalytic activities of the TMAI- and GSAI-based hybrids containing the N-terminus (residues 1-89) of BHAI were significantly enhanced by metals, but their thermostabilities were poor even in the presence of Mn(2+), indicating that the effects of metals on catalysis and thermostability involve different structural regions. Moreover, in contrast to the C-terminal truncate (Δ20 residues) of GSAI, the N-terminal truncate (Δ7 residues) exhibited no activity due to loss of its native structure. The data thus strongly suggest that the metal dependence of the catalysis and thermostability of hyperthermophilic AIs evolved separately to optimize their activity and thermostability at elevated temperatures. This may provide effective target regions for engineering, thereby meeting industrial demands for the production of d-tagatose.

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

Selective polymerization catalysis: controlling the metal chain end group to prepare block copolyesters.

Science.gov (United States)

Zhu, Yunqing; Romain, Charles; Williams, Charlotte K

2015-09-30

Selective catalysis is used to prepare block copolyesters by combining ring-opening polymerization of lactones and ring-opening copolymerization of epoxides/anhydrides. By using a dizinc complex with mixtures of up to three different monomers and controlling the chemistry of the Zn-O(polymer chain) it is possible to select for a particular polymerization route and thereby control the composition of block copolyesters.

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

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.

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 ...

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

Ferroelectrics: A pathway to switchable surface chemistry and catalysis

Science.gov (United States)

Kakekhani, Arvin; Ismail-Beigi, Sohrab; Altman, Eric I.

2016-08-01

It has been known for more than six decades that ferroelectricity can affect a material's surface physics and chemistry thereby potentially enhancing its catalytic properties. Ferroelectrics are a class of materials with a switchable electrical polarization that can affect surface stoichiometry and electronic structure and thus adsorption energies and modes; e.g., molecular versus dissociative. Therefore, ferroelectrics may be utilized to achieve switchable surface chemistry whereby surface properties are not fixed but can be dynamically controlled by, for example, applying an external electric field or modulating the temperature. Several important examples of applications of ferroelectric and polar materials in photocatalysis and heterogeneous catalysis are discussed. In photocatalysis, the polarization direction can control band bending at water/ferroelectric and ferroelectric/semiconductor interfaces, thereby facilitating charge separation and transfer to the electrolyte and enhancing photocatalytic activity. For gas-surface interactions, available results suggest that using ferroelectrics to support catalytically active transition metals and oxides is another way to enhance catalytic activity. Finally, the possibility of incorporating ferroelectric switching into the catalytic cycle itself is described. In this scenario, a dynamic collaboration of two polarization states can be used to drive reactions that have been historically challenging to achieve on surfaces with fixed chemical properties (e.g., direct NOx decomposition and the selective partial oxidation of methane). These predictions show that dynamic modulation of the polarization can help overcome some of the fundamental limitations on catalytic activity imposed by the Sabatier principle.

Rice husks as a sustainable silica source for hierarchical flower-like metal silicate architectures assembled into ultrathin nanosheets for adsorption and catalysis.

Science.gov (United States)

Zhang, Shouwei; Gao, Huihui; Li, Jiaxing; Huang, Yongshun; Alsaedi, Ahmed; Hayat, Tasawar; Xu, Xijin; Wang, Xiangke

2017-01-05

Metal silicates have attracted extensive interests due to their unique structure and promising properties in adsorption and catalysis. However, their applications were hampered by the complex and expensive synthesis. In this paper, three-dimensional (3D) hierarchical flower-like metal silicate, including magnesium silicate, zinc silicate, nickel silicate and cobalt silicate, were for the first time prepared by using rice husks as a sustainable silicon source. The flower-like morphology, interconnected ultrathin nanosheets structure and high specific surface area endowed them with versatile applications. Magnesium silicate was used as an adsorbent with the maximum adsorption capacities of 557.9, 381.3, and 482.8mg/g for Pb 2+ , tetracycline (TC), and UO 2 2+ , respectively. Ni nanoparticles/silica (Ni NPs/SiO 2 ) exhibited high catalytic activity and good stability for 4-nitrophenol (4-NP) reduction within only ∼160s, which can be attributed to the ultra-small particle size (∼6.8nm), good dispersion and high loading capacity of Ni NPs. Considering the abundance and renewability of rice husks, metal silicate with complex architecture can be easily produced at a large scale and become a sustainable and reliable resource for multifunctional applications. Copyright © 2016 Elsevier B.V. All rights reserved.

PREPARATIONS AND APPLICATION OF METAL NANOPARTICLES

Directory of Open Access Journals (Sweden)

Adlim Adlim

2010-06-01

Full Text Available Terminology of metal nanoparticles, the uniqueness properties in terms of the surface atom, the quantum dot, and the magnetism are described. The further elaboration was on the synthesis of nanoparticles. Applications of metal nanoparticles in electronic, ceramic medical and catalysis were overviewed. The bibliography includes 81 references with 99% are journal articles.   Keywords: metal nanoparticles

PREPARATIONS AND APPLICATION OF METAL NANOPARTICLES

OpenAIRE

Adlim, Adlim

2010-01-01

Terminology of metal nanoparticles, the uniqueness properties in terms of the surface atom, the quantum dot, and the magnetism are described. The further elaboration was on the synthesis of nanoparticles. Applications of metal nanoparticles in electronic, ceramic medical and catalysis were overviewed. The bibliography includes 81 references with 99% are journal articles.   Keywords: metal nanoparticles

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

Trace metals in antifouling paint particles and their heterogeneous contamination of coastal sediments

International Nuclear Information System (INIS)

Singh, Nimisha; Turner, Andrew

2009-01-01

Antifouling paint residues collected from the hard-standings of a marine leisure boat facility have been chemically characterised. Scanning electron microscopy revealed distinct layers, many containing oxidic particles of Cu and Zn. Quantitative analysis indicated concentrations of Cu and Zn averaging about 300 and 100 mg g -1 , respectively, and small proportions of these metals ( -1 , respectively. Estuarine sediment collected near a boatyard contained concentrations of Cu and Zn an order of magnitude greater than respective concentrations in 'background' sediment, and mass balance calculations suggested that the former sample was contaminated by about 1% by weight of paint particles. Clearly, antifouling residues represent a highly significant, heterogeneous source of metallic contamination in the marine environment where boating activities occur.

Modeling heat dissipation at the nanoscale: an embedding approach for chemical reaction dynamics on metal surfaces.

Science.gov (United States)

Meyer, Jörg; Reuter, Karsten

2014-04-25

We present an embedding technique for metallic systems that makes it possible to model energy dissipation into substrate phonons during surface chemical reactions from first principles. The separation of chemical and elastic contributions to the interaction potential provides a quantitative description of both electronic and phononic band structure. Application to the dissociation of O2 at Pd(100) predicts translationally "hot" oxygen adsorbates as a consequence of the released adsorption energy (ca. 2.6 eV). This finding questions the instant thermalization of reaction enthalpies generally assumed in models of heterogeneous catalysis. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solar-Powered Plasmon-Enhanced Heterogeneous Catalysis

Directory of Open Access Journals (Sweden)

Naldoni Alberto

2016-06-01

Full Text Available Photocatalysis uses semiconductors to convert sunlight into chemical energy. Recent reports have shown that plasmonic nanostructures can be used to extend semiconductor light absorption or to drive direct photocatalysis with visible light at their surface. In this review, we discuss the fundamental decay pathway of localized surface plasmons in the context of driving solar-powered chemical reactions. We also review different nanophotonic approaches demonstrated for increasing solar-to-hydrogen conversion in photoelectrochemical water splitting, including experimental observations of enhanced reaction selectivity for reactions occurring at the metalsemiconductor interface. The enhanced reaction selectivity is highly dependent on the morphology, electronic properties, and spatial arrangement of composite nanostructures and their elements. In addition, we report on the particular features of photocatalytic reactions evolving at plasmonic metal surfaces and discuss the possibility of manipulating the reaction selectivity through the activation of targeted molecular bonds. Finally, using solar-to-hydrogen conversion techniques as an example, we quantify the efficacy metrics achievable in plasmon-driven photoelectrochemical systems and highlight some of the new directions that could lead to the practical implementation of solar-powered plasmon-based catalytic devices.

Assessment of research needs for advanced heterogeneous catalysts for energy applications. Final report: Volume 2, Topic reports

Energy Technology Data Exchange (ETDEWEB)

Mills, G.A.

1994-04-01

This report assesses the direction, technical content, and priority of research needs judged to provide the best chance of yielding new and improved heterogeneous catalysts for energy-related applications over the period of 5-20 years. It addresses issues of energy conservation, alternate fuels and feedstocks, and the economics and applications that could alleviate pollution from energy processes. Recommended goals are defined in 3 research thrusts: catalytic science, environmental protection by catalysis, and industrial catalytic applications. This study was conducted by an 11-member panel of experts from industry and academia, including one each from Japan and Europe. This volume first presents an in-depth overview of the role of catalysis in future energy technology in chapter 1; then current catalytic research is critically reviewed and research recommended in 8 topic chapters: catalyst preparation (design and synthesis), catalyst characterization (structure/function), catalyst performance testing, reaction kinetics/reactor design, catalysis for industrial chemicals, catalysis for electrical applications (clean fuels, pollution remediation), catalysis for control of exhaust emissions, and catalysts for liquid transportation fuels from petroleum, coal, residual oil, and biomass.

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

KAUST Repository

Pelletier, Jeremie; Basset, Jean-Marie

2016-01-01

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

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.

Activities of Heterogeneous Acid-Base Catalysts for Fragrances Synthesis: A Review

Directory of Open Access Journals (Sweden)

Hartati Hartati

2013-06-01

Full Text Available This paper reviews various types of heterogeneous acid-base catalysts for fragrances preparation. Catalytic activities of various types of heterogeneous acid and base catalysts in fragrances preparation, i.e. non-zeolitic, zeolitic, and mesoporous molecular sieves have been reported. Generally, heterogeneous acid catalysts are commonly used in fragrance synthesis as compared to heterogeneous base catalysts. Heteropoly acids and hydrotalcites type catalysts are widely used as heterogeneous acid and base catalysts, respectively. © 2013 BCREC UNDIP. All rights reservedReceived: 20th January 2013; Revised: 31st March 2013; Accepted: 1st April 2013[How to Cite: Hartati, H., Santoso, M., Triwahyono, S., Prasetyoko, D. (2013. Activities of Heterogeneous Acid-Base Catalysts for Fragrances Synthesis: A Review. Bulletin of Chemical Reaction Engineering & Catalysis, 8 (1: 14-33. (doi:10.9767/bcrec.8.1.4394.14-33][Permalink/DOI: http://dx.doi.org/10.9767/bcrec.8.1.4394.14-33] | View in  |

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.

Heterogeneities in metallic glasses. Atomistic computer simulations on the structure and mechanical properties of copper-zirconium alloys and composites

International Nuclear Information System (INIS)

Brink, Tobias

2017-01-01

The present thesis deals with molecular dynamics computer simulations of heterogeneities in copper-zirconium metallic glasses, ranging from intrinsic structural fluctuations to crystalline secondary phases. These heterogeneities define, on a microscopic scale, the properties of the glass, and an understanding of their nature and behaviour is required for deriving the proper structure-property relations. In terms of composite systems, we start with the amorphisation of copper nanolayers embedded in a metallic glass matrix. While copper is an fcc metal with a high propensity for crystallisation, amorphisation can in fact occur in such systems for thermodynamic reasons. This is due to interface effects, which are also known from heterogeneous interfaces in crystals or from grain boundary complexions, although in absence of lattice mismatch. In single-phase glasses, intrinsic heterogeneities are often discussed in terms of soft spots or geometrically unfavourable motifs (GUMs), which can be considered to be mechanically weaker, defective regions of the glass. We investigate the relation between these motifs and the boson peak, an anomaly in the vibrational spectrum of all glasses. We demonstrate a relation between the boson peak and soft spots by analysing various amorphous and partially amorphous samples as well as highentropy alloys. Finally, we treat the plastic deformation of glasses, with and without crystalline secondary phases. We propose an explanation for the experimentally observed variations of propagation direction, composition, and density along a shear band. These variations of propagation direction are small in the case of single-phase glasses. A considerably greater influence on shear band propagation can be exerted by precipitates. We systematically investigate composites ranging from low crystalline volume fraction up to systems which resemble a nanocrystalline metal. In this context, we derive a mechanism map for composite systems and observe the

Heterogeneities in metallic glasses. Atomistic computer simulations on the structure and mechanical properties of copper-zirconium alloys and composites

Energy Technology Data Exchange (ETDEWEB)

Brink, Tobias

2017-07-01

The present thesis deals with molecular dynamics computer simulations of heterogeneities in copper-zirconium metallic glasses, ranging from intrinsic structural fluctuations to crystalline secondary phases. These heterogeneities define, on a microscopic scale, the properties of the glass, and an understanding of their nature and behaviour is required for deriving the proper structure-property relations. In terms of composite systems, we start with the amorphisation of copper nanolayers embedded in a metallic glass matrix. While copper is an fcc metal with a high propensity for crystallisation, amorphisation can in fact occur in such systems for thermodynamic reasons. This is due to interface effects, which are also known from heterogeneous interfaces in crystals or from grain boundary complexions, although in absence of lattice mismatch. In single-phase glasses, intrinsic heterogeneities are often discussed in terms of soft spots or geometrically unfavourable motifs (GUMs), which can be considered to be mechanically weaker, defective regions of the glass. We investigate the relation between these motifs and the boson peak, an anomaly in the vibrational spectrum of all glasses. We demonstrate a relation between the boson peak and soft spots by analysing various amorphous and partially amorphous samples as well as highentropy alloys. Finally, we treat the plastic deformation of glasses, with and without crystalline secondary phases. We propose an explanation for the experimentally observed variations of propagation direction, composition, and density along a shear band. These variations of propagation direction are small in the case of single-phase glasses. A considerably greater influence on shear band propagation can be exerted by precipitates. We systematically investigate composites ranging from low crystalline volume fraction up to systems which resemble a nanocrystalline metal. In this context, we derive a mechanism map for composite systems and observe the

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)

Supporting palladium metal on gold nanoparticles improves its catalysis for nitrite reduction.

Science.gov (United States)

Qian, Huifeng; Zhao, Zhun; Velazquez, Juan C; Pretzer, Lori A; Heck, Kimberly N; Wong, Michael S

2014-01-07

Nitrate (NO3(-)) and nitrite (NO2(-)) anions are often found in groundwater and surface water as contaminants globally, especially in agricultural areas due to nitrate-rich fertilizer use. One popular approach to studying the removal of nitrite/nitrate from water has been their degradation to dinitrogen via Pd-based reduction catalysis. However, little progress has been made towards understanding how the catalyst structure can improve activity. Focusing on the catalytic reduction of nitrite in this study, we report that Au NPs supporting Pd metal ("Pd-on-Au NPs") show catalytic activity that varies with volcano-shape dependence on Pd surface coverage. At room temperature, in CO2-buffered water, and under H2 headspace, the NPs were maximally active at a Pd surface coverage of 80%, with a first-order rate constant (k(cat) = 576 L g(Pd)(-1) min(-1)) that was 15x and 7.5x higher than monometallic Pd NPs (~4 nm; 40 L g(Pd)(-1) min(-1)) and Pd/Al2O3 (1 wt% Pd; 76 L g(Pd)(-1) min(-1)), respectively. Accounting only for surface Pd atoms, these NPs (576 L g(surface-Pd)(-1) min(-1)) were 3.6x and 1.6x higher than monometallic Pd NPs (160 L g(surface-Pd)(-1) min(-1)) and Pd/Al2O3 (361 L g(surface-Pd)(-1) min(-1)). These NPs retained ~98% of catalytic activity at a chloride concentration of 1 mM, whereas Pd/Al2O3 lost ~50%. The Pd-on-Au nanostructure is a promising approach to improve the catalytic reduction process for nitrite and, with further development, also for nitrate anions.

Mechanistic aspects of dinitrogen cleavage and hydrogenation to produce ammonia in catalysis and organometallic chemistry: relevance of metal hydride bonds and dihydrogen.

Science.gov (United States)

Jia, Hong-Peng; Quadrelli, Elsje Alessandra

2014-01-21

Dinitrogen cleavage and hydrogenation by transition-metal centers to produce ammonia is central in industry and in Nature. After an introductory section on the thermodynamic and kinetic challenges linked to N2 splitting, this tutorial review discusses three major classes of transition-metal systems (homogeneous, heterogeneous and biological) capable of achieving dissociation and hydrogenation of dinitrogen. Molecular complexes, solid-state Haber-Bosch catalytic systems, silica-supported tantalum hydrides and nitrogenase will be discussed. Emphasis is focused on the reaction mechanisms operating in the process of dissociation and hydrogenation of dinitrogen, and in particular on the key role played by metal hydride bonds and by dihydrogen in such reactions.

Metallic ions catalysis for improving bioleaching yield of Zn and Mn from spent Zn-Mn batteries at high pulp density of 10.

Science.gov (United States)

Niu, Zhirui; Huang, Qifei; Wang, Jia; Yang, Yiran; Xin, Baoping; Chen, Shi

2015-11-15

Bioleaching of spent batteries was often conducted at pulp density of 1.0% or lower. In this work, metallic ions catalytic bioleaching was used for release Zn and Mn from spent ZMBs at 10% of pulp density. The results showed only Cu(2+) improved mobilization of Zn and Mn from the spent batteries among tested four metallic ions. When Cu(2+) content increased from 0 to 0.8 g/L, the maximum release efficiency elevated from 47.7% to 62.5% for Zn and from 30.9% to 62.4% for Mn, respectively. The Cu(2+) catalysis boosted bioleaching of resistant hetaerolite through forming a possible intermediate CuMn2O4 which was subject to be attacked by Fe(3+) based on a cycle of Fe(3+)/Fe(2+). However, poor growth of cells, formation of KFe3(SO4)2(OH)6 and its possible blockage between cells and energy matters destroyed the cycle of Fe(3+)/Fe(2+), stopping bioleaching of hetaerolite. The chemical reaction controlled model fitted best for describing Cu(2+) catalytic bioleaching of spent ZMBs. Copyright © 2015 Elsevier B.V. All rights reserved.

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.

Catalytic olefin polymerization with early transition metal compounds

NARCIS (Netherlands)

Eshuis, Johan Jan Willem

1991-01-01

The catalysis of organic reactions by soluble metal complexes has become a major tool in synthesis, both in the laboratory and in the chemical industry. Processes catalyzed by transition metal complexes include carbonylation, olefin polymerization, olefin addition, olefin oxidation and alkane and

Chapter 19: Catalysis by Metal Carbides and Nitrides

Energy Technology Data Exchange (ETDEWEB)

Schaidle, Joshua A [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Nash, Connor P [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Yung, Matthew M [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Chen, Yuan [Pacific Northwest National Laboratory; Carl, Sarah [University of Michigan; Thompson, Levi [University of Michigan

2017-08-09

Early transition metal carbides and nitrides (ETMCNs), materials in which carbon or nitrogen occupies interstitial sites within a parent metal lattice, possess unique physical and chemical properties that motivate their use as catalysts. Specifically, these materials possess multiple types of catalytic sites, including metallic, acidic, and basic sites, and as such, exhibit reactivities that differ from their parent metals. Moreover, their surfaces are dynamic under reaction conditions. This chapter reviews recent (since 2010) experimental and computational investigations into the catalytic properties of ETMCN materials for applications including biomass conversion, syngas and CO2 upgrading, petroleum and natural gas refining, and electrocatalytic energy conversion, energy storage, and chemicals production, and attempts to link catalyst performance to active site identity/surface structure in order to elucidate the present level of understanding of structure-function relationships for these materials. The chapter concludes with a perspective on leveraging the unique properties of these materials to design and develop improved catalysts through a dedicated, multidisciplinary effort.

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.

Crystal Structure of (+)-[delta]-Cadinene Synthase from Gossypium arboreum and Evolutionary Divergence of Metal Binding Motifs for Catalysis

Energy Technology Data Exchange (ETDEWEB)

Gennadios, Heather A.; Gonzalez, Veronica; Di Costanzo, Luigi; Li, Amang; Yu, Fanglei; Miller, David J.; Allemann, Rudolf K.; Christianson, David W.; (UPENN); (Cardiff); (UC)

2009-09-11

(+)-{delta}-Cadinene synthase (DCS) from Gossypium arboreum (tree cotton) is a sesquiterpene cyclase that catalyzes the cyclization of farnesyl diphosphate in the first committed step of the biosynthesis of gossypol, a phytoalexin that defends the plant from bacterial and fungal pathogens. Here, we report the X-ray crystal structure of unliganded DCS at 2.4 {angstrom} resolution and the structure of its complex with three putative Mg{sup 2+} ions and the substrate analogue inhibitor 2-fluorofarnesyl diphosphate (2F-FPP) at 2.75 {angstrom} resolution. These structures illuminate unusual features that accommodate the trinuclear metal cluster required for substrate binding and catalysis. Like other terpenoid cyclases, DCS contains a characteristic aspartate-rich D{sup 307}DTYD{sup 311} motif on helix D that interacts with Mg{sub A}{sup 2+} and Mg{sub C}{sup 2+}. However, DCS appears to be unique among terpenoid cyclases in that it does not contain the 'NSE/DTE' motif on helix H that specifically chelates Mg{sub B}{sup 2+}, which is usually found as the signature sequence (N,D)D(L,I,V)X(S,T)XXXE (boldface indicates Mg{sub B}{sup 2+} ligands). Instead, DCS contains a second aspartate-rich motif, D{sup 451}DVAE{sup 455}, that interacts with Mg{sub B}{sup 2+}. In this regard, DCS is more similar to the isoprenoid chain elongation enzyme farnesyl diphosphate synthase, which also contains two aspartate-rich motifs, rather than the greater family of terpenoid cyclases. Nevertheless, the structure of the DCS-2F-FPP complex shows that the structure of the trinuclear magnesium cluster is generally similar to that of other terpenoid cyclases despite the alternative Mg{sub B}{sup 2+} binding motif. Analyses of DCS mutants with alanine substitutions in the D{sup 307}DTYD{sup 311} and D{sup 451}DVAE{sup 455} segments reveal the contributions of these segments to catalysis.

An efficient solvent-free synthesis of imidazolines and benzimidazoles using K 4[Fe(CN 6] catalysis

Directory of Open Access Journals (Sweden)

Kabeer A. Shaikh

2012-01-01

Full Text Available Imidazolines and Benzimidazoles have been efficiently synthesized in high yields by treatment of 1,2-diamine with aldehydes using the metal co-ordinate complex K 4[Fe(CN 6] as a catalysis. The method was carried out under solvent free condition via oxidation of carbon-nitrogen bond. The process is green, mild and inexpensive.

Metal- and Carbon-Based Materials as Heterogeneous Electrocatalysts for CO₂ Reduction.

Science.gov (United States)

Khan, Azam; Ullah, Haseeb; Nasir, Jamal Abdul; Shuda, Suzanne; Chen, Wei; Khan, M Abdullah

2018-05-01

Climate change caused by continuous rising level of CO2 and the depletion of fossil fuels reserves has made it highly desirable to electrochemically convert CO2 into fuels and commodity chemicals. Implementing this approach will close the carbon cycle by recycling CO2 providing a sustainable way to store energy in the chemical bonds of portable molecular fuels. In order to make the process commercially viable, the challenge of slow kinetics of CO2 electroreduction and low energy efficiency of the process need to be addressed. To this end, this review summarizes the progress made in the past few years in the development of heterogeneous electrocatalysts with a focus on nanostructured material for CO2 reduction to CO, HCOOH/HCOO-, CH2O, CH4, H2C2O4/HC2O-4, C2H4, CH3OH, CH3CH2OH, etc. The electrocatalysts presented here are classified into metals, metal alloys, metal oxides, metal chalcogenides and carbon based materials on the basis of their elemental composition, whose performance is discussed in light of catalyst activity, product selectivity, Faradaic efficiency (FE), catalytic durability and in selected cases mechanism of CO2 electroreduction. The effect of particle size, morphology and solution-electrolyte type and composition on the catalyst property/activity is also discussed and finally some strategies are proposed for the development of CO2 electroreduction catalysts. The aim of this article is to review the recent advances in the field of CO2 electroreduction in order to further facilitate research and development in this area.

Yeast enolase: mechanism of activation by metal ions.

Science.gov (United States)

Brewer, J M

1981-01-01

Yeast enolase as prepared by current procedures is inherently chemically homogeneous, though deamidation and partial denaturation can produce electrophoretically distinct forms. A true isozyme of the enzyme exists but does not survive the purification procedure. The chemical sequence for both has been established. The enzyme behaves in solution like a compact, nearly spherical molecule of moderate hydration. Strong intramolecular forces maintain the structure of the individual subunits. The enzyme as isolated is dimeric. If dissociated in the presence of magnesium ions and substrate, then the subunits are active, but if the dissociation occurs in the absence of metal ions, they are inactive until they have reassociated and undergone a first order "annealing" process. Magnesium (II) enhances association. The interaction between the subunits is hydrophobic in character. The enzyme can bind up to 2 mol of most metal ions in "conformational" sites which then allows up to 2 mol of substrate or some substrate analogue to bind. This is not sufficient for catalysis, but conformational metal ions do more than just allow substrate binding. A change in the environment of the metal ions occurs on substrate or substrate analogue binding. There is an absolute correlation between the occurrence of a structural change undergone by the 3-amino analogue of phosphoenolpyruvate and whether the metal ions produce any level of enzymatic activity. For catalysis, two more moles of metal ions, called "catalytic", must bind. There is evidence that the enzymatic reaction involves a carbanion mechanism. It is likely that two more moles of metal ion can bind which inhibit the reaction. The requirement for 2 mol of metal ion per subunit which contribute in different ways to catalysis is exhibited by a number of other enzymes.

Combining X-ray Absorption and X-ray Diffraction Techniques for in Situ Studies of Chemical Transformations in Heterogeneous Catalysis: Advantages and Limitations

International Nuclear Information System (INIS)

Frenkel, A.I.; Hanson, J.; Wang, Q.; Marinkovic, N.; Chen, J.G.; Barrio, L.; Si, R.; Lopez Camara, A.; Estrella, A.M.; Rodriguez, J.A.

2011-01-01

Recent advances in catalysis instrumentations include synchrotron-based facilities where time-resolved X-ray scattering and absorption techniques are combined in the same in situ or operando experiment to study catalysts at work. To evaluate the advances and limitations of this method, we performed a series of experiments at the new XAFS/XRD instrument in the National Synchrotron Light Source. Nearly simultaneous X-ray diffraction (XRD) and X-ray absorption fine-structure (XAFS) measurements of structure and kinetics of several catalysts under reducing or oxidizing conditions have been performed and carefully analyzed. For CuFe 2 O 4 under reducing conditions, the combined use of the two techniques allowed us to obtain accurate data on kinetics of nucleation and growth of metallic Cu. For the inverse catalyst CuO/CeO 2 that underwent isothermal reduction (with CO) and oxidation (with O 2 ), the XAFS data measured in the same experiment with XRD revealed strongly disordered Cu species that went undetected by diffraction. These and other examples emphasize the unique sensitivity of these two complementary methods to follow catalytic processes in the broad ranges of length and time scales.

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.

Assembly, Structure, and Functionality of Metal-Organic Networks and Organic Semiconductor Layers at Surfaces

Science.gov (United States)

Tempas, Christopher D.

Self-assembled nanostructures at surfaces show promise for the development of next generation technologies including organic electronic devices and heterogeneous catalysis. In many cases, the functionality of these nanostructures is not well understood. This thesis presents strategies for the structural design of new on-surface metal-organic networks and probes their chemical reactivity. It is shown that creating uniform metal sites greatly increases selectivity when compared to ligand-free metal islands. When O2 reacts with single-site vanadium centers, in redox-active self-assembled coordination networks on the Au(100) surface, it forms one product. When O2 reacts with vanadium metal islands on the same surface, multiple products are formed. Other metal-organic networks described in this thesis include a mixed valence network containing Pt0 and PtII and a network where two Fe centers reside in close proximity. This structure is stable to temperatures >450 °C. These new on-surface assemblies may offer the ability to perform reactions of increasing complexity as future heterogeneous catalysts. The functionalization of organic semiconductor molecules is also shown. When a few molecular layers are grown on the surface, it is seen that the addition of functional groups changes both the film's structure and charge transport properties. This is due to changes in both first layer packing structure and the pi-electron distribution in the functionalized molecules compared to the original molecule. The systems described in this thesis were studied using high-resolution scanning tunneling microscopy, non-contact atomic force microscopy, and X-ray photoelectron spectroscopy. Overall, this work provides strategies for the creation of new, well-defined on-surface nanostructures and adds additional chemical insight into their properties.

Degradation of organic dyes by a new heterogeneous Fenton reagent - Fe2GeS4 nanoparticle.

Science.gov (United States)

Shi, Xiaoguo; Tian, Ang; You, Junhua; Yang, He; Wang, Yuzheng; Xue, Xiangxin

2018-07-05

The heterogeneous Fenton system has become the hotspot in the decontamination field due to its effective degradation performance with a wide pH range. Based on the unstable chemical properties of pyrite, in this article, Fe 2 GeS 4 nanoparticles with better thermodynamic stability were prepared by vacuum sintering and high energy ball milling and its potential as Fenton reagent was investigated for the first time. Three determinants of the heterogeneous Fenton system including the iron source, hydrogen peroxide, pH and the degradation mechanism were investigated. The catalyst dosage of 0.3 g/L, initial H 2 O 2 concentration in the Fenton system of 50 m mol/L and pH of 7 were chosen as the best operational conditions. An almost complete degradation was achieved within 5 min for methylene blue and rhodamine b while 10 min for methyl orange. The total organic carbon removal efficiencies of Fe 2 GeS 4 heterogeneous Fenton system for methylene blue, methyl orange and rhodamine b in 10 min were 56.3%, 66.2% and 74.2%, respectively. It's found that the degradation ability could be attributed to a heterogeneous catalysis occurring at the Fe 2 GeS 4 surface together with a homogeneous catalysis in the aqueous phase by the dissolved iron ions. Copyright © 2018 Elsevier B.V. All rights reserved.

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.

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

Nanoscale heterogeneity at the aqueous electrolyte-electrode interface

Science.gov (United States)

Limmer, David T.; Willard, Adam P.

2015-01-01

Using molecular dynamics simulations, we reveal emergent properties of hydrated electrode interfaces that while molecular in origin are integral to the behavior of the system across long times scales and large length scales. Specifically, we describe the impact of a disordered and slowly evolving adsorbed layer of water on the molecular structure and dynamics of the electrolyte solution adjacent to it. Generically, we find that densities and mobilities of both water and dissolved ions are spatially heterogeneous in the plane parallel to the electrode over nanosecond timescales. These and other recent results are analyzed in the context of available experimental literature from surface science and electrochemistry. We speculate on the implications of this emerging microscopic picture on the catalytic proficiency of hydrated electrodes, offering a new direction for study in heterogeneous catalysis at the nanoscale.

Atomic layer deposition of highly dispersed Pt nanoparticles on a high surface area electrode backbone for electrochemical promotion of catalysis

NARCIS (Netherlands)

Hajar, Y.; di Palma, V.; Kyriakou, V.; Verheijen, M. A.; Baranova, E. A.; Vernoux, P.; Kessels, W. M. M.; Creatore, M.; van de Sanden, M. C. M.; Tsampas, M. N.

2017-01-01

A novel catalyst design for electrochemical promotion of catalysis (EPOC) is proposed which overcomes the main bottlenecks that limit EPOC commercialization, i.e., the low dispersion and small surface area of metal catalysts. We have increased the surface area by using a porous composite electrode

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.

Mass spectrometric production of heterogeneous metal clusters using Knudsen cell

Directory of Open Access Journals (Sweden)

Veljković Filip M.

2016-01-01

Full Text Available Knudsen effusion mass spectrometry or high-temperature method of mass spectrometry for decades gives new information about saturated vapor of hardly volatile compounds and it is an important method in the discovery of many new molecules, radicals, ions and clusters present in the gas phase. Since pioneering works until now, this method has been successfully applied to a large number of systems (ores, oxides, ceramics, glass materials, borides, carbides, sulfides, nitrates, metals, fullerenes, etc which led to the establishment of various research branches such as chemistry of clusters. This paper describes the basic principles of Knudsen cell use for both identification of chemical species created in the process of evaporation and determination of their ionization energies. Depending on detected ions intensities and the partial pressure of each gaseous component, as well as on changes in partial pressure with temperature, Knudsen cell mass spectrometry enables the determination of thermodynamic parameters of the tested system. A special attention is paid to its application in the field of small heterogeneous and homogeneous clusters of alkali metals. Furthermore, experimental results for thermodynamic parameters of some clusters, as well as capabilities of non-standard ways of using Knudsen cells in the process of synthesis of new clusters are presented herein. [Projekat Ministarstva nauke Republike Srbije, br. 172019

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.

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)

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

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.

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

Understanding the Enhanced Catalytic Performance of Ultrafine Transition Metal Nanoparticles–Graphene Composites

KAUST Repository

Liu, Xin; Meng, Changgong; Han, Yu

2015-01-01

, manufacture of chemicals, medicine synthesis, etc. Rational design and fabrication of highly efficient catalysts have become the ultimate goal of today's catalysis research. For the purpose of handling and product separation, heterogeneous catalysts are highly

Camphor as Chiral Motif in Ligand Design - Applications in Catalysis and Complexation Gas-Chromatography

OpenAIRE

Spallek, Markus Jürgen

2012-01-01

This thesis is intended to further extend the scope of camphor and camphor-derived building blocks in the synthesis of chiral ligands, catalysts and selectors, their successful application in catalysis and in enantioseparation sciences. The thesis is divided into four independent chapters each focusing on the development of novel camphor-based compounds and their application as catalysts or metal-selectors. A short introduction is given for each chapter dealing with recent progress in the fie...

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

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.

State equations and stability of shock wave fronts in homogeneous and heterogeneous metallic medium

International Nuclear Information System (INIS)

Romain, Jean-Pierre

1977-01-01

This research thesis in physical sciences reports a theoretical and experimental study of some mechanical and thermodynamic aspects related to a shock wave propagation in homogeneous and heterogeneous metallic media: state equations, stability and instability of shock wave fronts. In the first part, the author reports the study of the Grueneisen coefficient for some metallic elements with known static and dynamic compression properties. The second part reports the experimental investigation of dynamic compressibility of some materials (lamellar Al-Cu compounds). The front shock wave propagation has been visualised, and experimental Hugoniot curves are compared with those deduced from a developed numeric model and other models. The bismuth Hugoniot curve is also determined, and the author compares the existence and nature of phase transitions obtained by static and dynamic compression

[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.

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.

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.

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.

Metal-free carbon materials-catalyzed sulfate radical-based advanced oxidation processes: A review on heterogeneous catalysts and applications.

Science.gov (United States)

Zhao, Qingxia; Mao, Qiming; Zhou, Yaoyu; Wei, Jianhong; Liu, Xiaocheng; Yang, Junying; Luo, Lin; Zhang, Jiachao; Chen, Hong; Chen, Hongbo; Tang, Lin

2017-12-01

In recent years, advanced oxidation processes (AOPs), especially sulfate radical based AOPs have been widely used in various fields of wastewater treatment due to their capability and adaptability in decontamination. Recently, metal-free carbon materials catalysts in sulfate radical production has been more and more concerned because these materials have been demonstrated to be promising alternatives to conventional metal-based catalysts, but the review of metal-free catalysts is rare. The present review outlines the current state of knowledge on the generation of sulfate radical using metal-free catalysts including carbon nanotubes, graphene, mesoporous carbon, activated carbon, activated carbon fiber, nanodiamond. The mechanism such as the radical pathway and non-radical pathway, and factors influencing of the activation of sulfate radical was also be revealed. Knowledge gaps and research needs have been identified, which include the perspectives on challenges related to metal-free catalyst, heterogeneous metal-free catalyst/persulfate systems and their potential in practical environmental remediation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Metal-mediated aminocatalysis provides mild conditions: Enantioselective Michael addition mediated by primary amino catalysts and alkali-metal ions

Directory of Open Access Journals (Sweden)

Matthias Leven

2013-01-01

Full Text Available Four catalysts based on new amides of chiral 1,2-diamines and 2-sulfobenzoic acid have been developed. The alkali-metal salts of these betaine-like amides are able to form imines with enones, which are activated by Lewis acid interaction for nucleophilic attack by 4-hydroxycoumarin. The addition of 4-hydroxycoumarin to enones gives ee’s up to 83% and almost quantitative yields in many cases. This novel type of catalysis provides an effective alternative to conventional primary amino catalysis were strong acid additives are essential components.

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.

Understanding the mechanism of catalytic fast pyrolysis by unveiling reactive intermediates in heterogeneous catalysis

Science.gov (United States)

Hemberger, Patrick; Custodis, Victoria B. F.; Bodi, Andras; Gerber, Thomas; van Bokhoven, Jeroen A.

2017-06-01

Catalytic fast pyrolysis is a promising way to convert lignin into fine chemicals and fuels, but current approaches lack selectivity and yield unsatisfactory conversion. Understanding the pyrolysis reaction mechanism at the molecular level may help to make this sustainable process more economic. Reactive intermediates are responsible for product branching and hold the key to unveiling these mechanisms, but are notoriously difficult to detect isomer-selectively. Here, we investigate the catalytic pyrolysis of guaiacol, a lignin model compound, using photoelectron photoion coincidence spectroscopy with synchrotron radiation, which allows for isomer-selective detection of reactive intermediates. In combination with ambient pressure pyrolysis, we identify fulvenone as the central reactive intermediate, generated by catalytic demethylation to catechol and subsequent dehydration. The fulvenone ketene is responsible for the phenol formation. This technique may open unique opportunities for isomer-resolved probing in catalysis, and holds the potential for achieving a mechanistic understanding of complex, real-life catalytic processes.

Accurate Experimental and Theoretical Enthalpies of Association of TiCl4 with Typical Lewis Bases Used in Heterogeneous Ziegler-Natta Catalysis

KAUST Repository

Credendino, Raffaele

2017-09-18

Adducts of TiCl4 with Lewis bases used as internal or external donors in heterogeneous Ziegler-Natta (ZN) catalysis represents a fundamental interaction contributing to the final composition of MgCl2 supported ZN-catalysts. This study presents the accurate experimental evaluation, from titration calorimetry, of the formation enthalpy of TiCl4 adducts with 15 Lewis bases of industrial interests. In addition, we report accurate energies of association of TiCl4 with the same Lewis bases from calculations at the DLPNO-CCSD(T) level of theory. These accurate experimental and theoretical association values are compared with selected methods based on density functional theory (DFT) in combination with popular continuum solvation models. Calculations suggest that the PBE-D3, and M06 functionals in combination with a triple-ζ plus polarization quality basis set provide the best performance when the basis set superposition error (BSSE) is not removed from the association energies. Cleaning the association energies by the BSSE with the counterpoise protocol suggests the B3LYP-D3, TPSS-D3 and M06L as the best performing functionals. Introducing solvent effects with the PCM and SMD continuum solvation models allows comparing the DFT based association enthalpies with the experimental values obtained from titration calorimetry. Both solvation models in combination with the PBE-D3, PBE0-D3, B3LYP-D3, TPSS-D3, M06L, and M06 functionals provide association enthalpies close to the experimental values with MUEs in range 10 – 15 kJ/mol.

Sulfated tin oxide (STO – Structural properties and application in catalysis: A review

Directory of Open Access Journals (Sweden)

Ravi Varala

2016-07-01

Full Text Available Catalysis is an important area of chemistry, with an extensive amount of work going on in this area of sciences, toward synthesis and evaluation of newer catalysts. There are many reports for different conversion reactions such as oxidation, reduction, coupling, alkylation, and acylation for which various catalysts have been used such as mixed metal oxides, metal nanoparticles, metal organic complexes and many others. Among the many catalysts reported, the one catalyst that caught our attention due to its exploitation for a plethora of organic conversions is the sulfated tin oxide (STO, which is due to the low cost, greater stability and high efficiency of the catalyst. In this review, we have attempted to compile data about the structural properties of STO, and its applications as catalysts in various organic synthesis are presented. The literature data up to 2014 were collected and considered for the review.

C-C Coupling on Single-Atom-Based Heterogeneous Catalyst.

Science.gov (United States)

Zhang, Xiaoyan; Sun, Zaicheng; Wang, Bin; Tang, Yu; Nguyen, Luan; Li, Yuting; Tao, Franklin Feng

2018-01-24

Compared to homogeneous catalysis, heterogeneous catalysis allows for ready separation of products from the catalyst and thus reuse of the catalyst. C-C coupling is typically performed on a molecular catalyst which is mixed with reactants in liquid phase during catalysis. This homogeneous mixing at a molecular level in the same phase makes separation of the molecular catalyst extremely challenging and costly. Here we demonstrated that a TiO 2 -based nanoparticle catalyst anchoring singly dispersed Pd atoms (Pd 1 /TiO 2 ) is selective and highly active for more than 10 Sonogashira C-C coupling reactions (R≡CH + R'X → R≡R'; X = Br, I; R' = aryl or vinyl). The coupling between iodobenzene and phenylacetylene on Pd 1 /TiO 2 exhibits a turnover rate of 51.0 diphenylacetylene molecules per anchored Pd atom per minute at 60 °C, with a low apparent activation barrier of 28.9 kJ/mol and no cost of catalyst separation. DFT calculations suggest that the single Pd atom bonded to surface lattice oxygen atoms of TiO 2 acts as a site to dissociatively chemisorb iodobenzene to generate an intermediate phenyl, which then couples with phenylacetylenyl bound to a surface oxygen atom. This coupling of phenyl adsorbed on Pd 1 and phenylacetylenyl bound to O ad of TiO 2 forms the product molecule, diphenylacetylene.

Transition metal mediated transformations of small molecules

Energy Technology Data Exchange (ETDEWEB)

Sen, Ayusman [Pennsylvania State Univ., University Park, PA (United States)

2017-03-08

Catalysis at metal centers is of great scientific, as well as practical, importance because of the high efficiency, high specificity, and low energy demands often associated with such systems. The two major themes of our research are (a) the design of metal-based systems for the synthesis of novel classes of polymers and (b) the identification of new metal-catalyzed systems for the conversion of biomass to fuels and chemicals, and related “green” chemical processes.

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

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...

Confined-interface-directed synthesis of Palladium single-atom catalysts on graphene/amorphous carbon

DEFF Research Database (Denmark)

Xi, Jiangbo; Sun, Hongyu; Zhang, Zheye

2018-01-01

The maximized atomic efficiency of supported catalysts is highly desired in heterogeneous catalysis. Therefore, the design and development of active, stable, and atomic metal-based catalysts remains a formidable challenge. To tackle these problems, it is necessary to investigate the interaction b...

Architectural design of heterogeneous metallic nanocrystals--principles and processes.

Science.gov (United States)

Yu, Yue; Zhang, Qingbo; Yao, Qiaofeng; Xie, Jianping; Lee, Jim Yang

2014-12-16

CONSPECTUS: Heterogeneous metal nanocrystals (HMNCs) are a natural extension of simple metal nanocrystals (NCs), but as a research topic, they have been much less explored until recently. HMNCs are formed by integrating metal NCs of different compositions into a common entity, similar to the way atoms are bonded to form molecules. HMNCs can be built to exhibit an unprecedented architectural diversity and complexity by programming the arrangement of the NC building blocks ("unit NCs"). The architectural engineering of HMNCs involves the design and fabrication of the architecture-determining elements (ADEs), i.e., unit NCs with precise control of shape and size, and their relative positions in the design. Similar to molecular engineering, where structural diversity is used to create more property variations for application explorations, the architectural engineering of HMNCs can similarly increase the utility of metal NCs by offering a suite of properties to support multifunctionality in applications. The architectural engineering of HMNCs calls for processes and operations that can execute the design. Some enabling technologies already exist in the form of classical micro- and macroscale fabrication techniques, such as masking and etching. These processes, when used singly or in combination, are fully capable of fabricating nanoscopic objects. What is needed is a detailed understanding of the engineering control of ADEs and the translation of these principles into actual processes. For simplicity of execution, these processes should be integrated into a common reaction system and yet retain independence of control. The key to architectural diversity is therefore the independent controllability of each ADE in the design blueprint. The right chemical tools must be applied under the right circumstances in order to achieve the desired outcome. In this Account, after a short illustration of the infinite possibility of combining different ADEs to create HMNC design

Heterogeneous catalysis afford biodiesel of babassu, castor oil and blends

International Nuclear Information System (INIS)

Carvalho, Lee M.G. de; Abreu, Wiury C. de; Silva, Maria das Gracas de O. e; Matos, Jose Milton E. de; Moura, Carla V.R. de; Moura, Edmilson M. de; Lima, Jose Renato de O.; Oliveira, Jose Eduardo de

2013-01-01

This work describes the preparation of babassu, castor oil biodiesel and mixtures in various proportions of these oils, using alkaline compounds of strontium (SrCO 3 + SrO + Sr (OH) 2 ) as heterogeneous catalysts. The mixture of oils of these oleaginous sources was used in the production of biodiesel with quality parameters that meet current legislation. The catalyst was characterized by X-ray diffractometry (XDR), physisorption of gas (BET method), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDX) and Fourier transform infrared spectroscopy (FTIR). The viscometric technique was used to monitor the optimization.The transesterification reactions performed using strontium compounds reached conversion rates of 97.2% babassu biodiesel (BB), 96.4% castor oil biodiesel (COB) and 95.3% Babassu/Castor Oil Biodiesel 4:1 (BBCO41). (author)

Residual waters treatment by heterogeneous photocatalysis: a study of experimental parameters applied to the photoelectrocatalysis

Directory of Open Access Journals (Sweden)

Henrique de Santana

2006-02-01

Full Text Available In this paper, the use of electrochemically-assisted heterogeneous photo-catalysis will be discussed. Several operational parameters will also be discussed, in order to achieve optimum efficiency of this photo-degradation system, such as: the influence of variables as support electrolyte, applied potential, dye initial concentration, pH and choice of a UV source on dye degradation.

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...

Proceedings of the symposium on chemistry and physics of surface of metals and their oxides

Energy Technology Data Exchange (ETDEWEB)

1976-01-01

Topics covered include: structure of crystalline surfaces; thermodynamic, electrostatic, and physicochemical considerations on defect structure and metal to metal interfaces; physical properties of metal surfaces; stress corrosion cracking; corrosion; passivation; mass transfer across interfaces; electrodeposition; Auger electron spectroscopy; electron microscopy; and catalysis. (GHT)

Towards an atomic level understanding of niobia based catalysts and catalysis by combining the science of catalysis with surface science

Directory of Open Access Journals (Sweden)

Martin Schmal

2009-06-01

Full Text Available The science of catalysis and surface science have developed, independently, key information for understanding catalytic processes. One might argue: is there anything fundamental to be discovered through the interplay between catalysis and surface science? Real catalysts of monometallic and bimetallic Co/Nb2O5 and Pd-Co/Nb2O5 catalysts showed interesting selectivity results on the Fischer-Tropsch synthesis (Noronha et al. 1996, Rosenir et al. 1993. The presence of a noble metal increased the C+5 selectivity and decreased the methane formation depending of the reduction temperature. Model catalyst of Co-Pd supported on niobia and alumina were prepared and characterized at the atomic level, thus forming the basis for a comparison with "real" support materials. Growth, morphology and structure of both pure metal and alloy particles were studied. It is possible to support the strong metal support interaction suggested by studies on real catalysts via the investigation of model systems for niobia in comparison to alumina support in which this effect does not occur. Formation of Co2+ penetration into the niobia lattice was suggested on the basis of powder studies and can be fully supported on the basis of model studies. It is shown for both real catalysts and model systems that oxidation state of Co plays a key role in controlling the reactivity in Fischer-Tropsch reactions systems and that the addition of Pd is a determining factor for the stability of the catalyst. It is demonstrated that the interaction with unsaturated hydrocarbons depends strongly on the state of oxidation.As ciências da catálise e da superfície têm desenvolvido independentemente temas básicos para o entendimento de processos catalíticos. Pode-se até questionar se há ainda algo fundamental para ser descoberto através da interface entre catálise eciência da superfície? Catalisadores mono e bimetálicos de Co/Nb2O5 e Pd-Co/ Nb2O5 apresentaram resultados interessantes de

A review on versatile applications of transition metal complexes incorporating Schiff bases

Directory of Open Access Journals (Sweden)

Ahmed M. Abu-Dief

2015-06-01

Full Text Available Schiff bases and their complexes are versatile compounds synthesized from the condensation of an amino compound with carbonyl compounds and widely used for industrial purposes and also exhibit a broad range of biological activities including antifungal, antibacterial, antimalarial, antiproliferative, anti-inflammatory, antiviral, and antipyretic properties. Many Schiff base complexes show excellent catalytic activity in various reactions and in the presence of moisture. Over the past few years, there have been many reports on their applications in homogeneous and heterogeneous catalysis. The high thermal and moisture stabilities of many Schiff base complexes were useful attributes for their application as catalysts in reactions involving at high temperatures. The activity is usually increased by complexation therefore to understand the properties of both ligands and metal can lead to the synthesis of highly active compounds. The influence of certain metals on the biological activity of these compounds and their intrinsic chemical interest as multidentate ligands has prompted a considerable increase in the study of their coordination behaviour. Development of a new chemotherapeutic Schiff bases and their metal complexes is now attracting the attention of medicinal chemists. This review compiles examples of the most promising applied Schiff bases and their complexes in different areas.

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.

Catalysis and Downsizing in Mg-Based Hydrogen Storage Materials

Directory of Open Access Journals (Sweden)

Jianding Li

2018-02-01

Full Text Available Magnesium (Mg-based materials are promising candidates for hydrogen storage due to the low cost, high hydrogen storage capacity and abundant resources of magnesium for the realization of a hydrogen society. However, the sluggish kinetics and strong stability of the metal-hydrogen bonding of Mg-based materials hinder their application, especially for onboard storage. Many researchers are devoted to overcoming these challenges by numerous methods. Here, this review summarizes some advances in the development of Mg-based hydrogen storage materials related to downsizing and catalysis. In particular, the focus is on how downsizing and catalysts affect the hydrogen storage capacity, kinetics and thermodynamics of Mg-based hydrogen storage materials. Finally, the future development and applications of Mg-based hydrogen storage materials is discussed.

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.

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.

New Concept of C–H and C–C Bond Activation via Surface Organometallic Chemistry

KAUST Repository

Samantaray, Manoja

2015-08-18

In this chapter we describe the recent applications of well-defined oxidesupported metal alkyls/alkylidenes/alkylidynes and hydrides of group IV, V, and VI transition metals in the field of C–H and C–C bond activation. The activation of ubiquitous C–H and C–C bonds of paraffin is a long-standing challenge because of intrinsic low reactivity. There are many concepts derived from surface organometallic chemistry (SOMC): surface organometallic fragments are always intermediates in heterogeneous catalysis. The study of their synthesis and reactivity is a way to rationalize mechanism of heterogeneous catalysis and to achieve structure activity relationship. By surface organometallic chemistry one can enter any catalytic center by a reaction intermediate leading in fine to single site catalysts. With surface organometallic chemistry one can coordinate to the metal which can play a role in different elementary steps leading for example to C–H activation and Olefin metathesis. Because of the development of SOMC there is a lot of space for the improvement of homogeneous catalysis. After the 1997 discovery of alkane metathesis using silica-supported tantalum hydride by Basset et al. at low temperature (150ºC) the focus in this area was shifted to the discovery of more and more challenging surface complexes active in the application of C–H and C–C bond activation. Here we describe the evolution of well-defined metathesis catalyst with time as well as the effect of support on catalysis. We also describe here which metal–ligand combinations are responsible for a variety of C–H and C–C bond activation.

Density functional theory in surface chemistry and catalysis

DEFF Research Database (Denmark)

Nørskov, Jens Kehlet; Abild-Pedersen, Frank; Studt, Felix

2011-01-01

Recent advances in the understanding of reactivity trends for chemistry at transition-metal surfaces have enabled in silico design of heterogeneous catalysts in a few cases. The current status of the field is discussed with an emphasis on the role of coupling theory and experiment and future...

Heterogeneous catalysis afford biodiesel of babassu, castor oil and blends

Energy Technology Data Exchange (ETDEWEB)

Carvalho, Lee M.G. de; Abreu, Wiury C. de; Silva, Maria das Gracas de O. e; Matos, Jose Milton E. de; Moura, Carla V.R. de; Moura, Edmilson M. de, E-mail: mmoura@ufpi.edu.br [Universidade Federal do Piaui (UFPI), Teresina, PI (Brazil). Departamento de Quimica; Lima, Jose Renato de O.; Oliveira, Jose Eduardo de [Universidade Estadual Paulista Julio de Mesquita Filho (UNESP/IQ/CEMPEQC), Araraquara, SP (Brazil). Instituto de Quimica. Centro de Monitoramento e Pesquisa da Qualidade de Combustiveis, Biocombustiveis, Petroleo e Derivados

2013-04-15

This work describes the preparation of babassu, castor oil biodiesel and mixtures in various proportions of these oils, using alkaline compounds of strontium (SrCO{sub 3} + SrO + Sr (OH){sub 2}) as heterogeneous catalysts. The mixture of oils of these oleaginous sources was used in the production of biodiesel with quality parameters that meet current legislation. The catalyst was characterized by X-ray diffractometry (XDR), physisorption of gas (BET method), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDX) and Fourier transform infrared spectroscopy (FTIR). The viscometric technique was used to monitor the optimization.The transesterification reactions performed using strontium compounds reached conversion rates of 97.2% babassu biodiesel (BB), 96.4% castor oil biodiesel (COB) and 95.3% Babassu/Castor Oil Biodiesel 4:1 (BBCO41). (author)

Surface-structure dependence of water-related adsorbates on platinum

NARCIS (Netherlands)

Badan, C.

2016-01-01

Today, the energy sector is highly dependent on heterogeneous catalysis because a future solution to end our dependency on natural sources lies in generating hydrogen by splitting water. Several transition metals, such as Pt, are known to be good catalyst materials for water splitting reactions.

Preparation and characterization of nanostructured metal oxides for application to biomass upgrading Polar (111) metal oxide surfaces for pyrolysis oil upgrading and lignin depolymerization

Science.gov (United States)

Finch, Kenneth

2013-01-01

Pyrolysis oil, or bio-oil, is one of the most promising methods to upgrade a variety of biomass to transportation fuels. Moving toward a more "green" catalytic process requires heterogeneous catalysis over homogeneous catalysis to avoid extraction solvent waste. Nanoscale catalysts are showing great promise due to their high surface area and unusual surfaces. Base catalyzed condensation reactions occur much quicker than acid catalyzed condensation reactions. However, MgO is slightly soluble in water and is susceptible to degradation by acidic environments, similar to those found in fast-pyrolysis oil. Magnesium oxide (111) has a highly active Lewis base surface, which can catalyze Claisen-Schmidt condensation reactions in the organic phase. It has been shown previously that carbon coating a catalyst, such as a metal oxide, provides integrity while leaving the catalytic activity intact. Here, carbon-coated MgO(111) will be discussed with regards to synthesis, characterization and application to bio-oil upgrading through model compounds. Raman spectroscopy and HR-TEM are used to characterize the thickness and carbon-bonding environment of the carbon coating. Propanal self-condensation reactions have been conducted in the aqueous phase with varying amounts of acetic acid present. Quantitative analysis by gas chromatography was completed to determine the catalytic activity of CC-MgO(111). ICP-OES analysis has been conducted to measure the magnesium concentration in the product solution and give insight into the leaching of the catalyst into the reaction solution.

Marvels of enzyme catalysis at true atomic resolution: distortions, bond elongations, hidden flips, protonation states and atom identities.

Science.gov (United States)

Neumann, Piotr; Tittmann, Kai

2014-12-01

Although general principles of enzyme catalysis are fairly well understood nowadays, many important details of how exactly the substrate is bound and processed in an enzyme remain often invisible and as such elusive. In fortunate cases, structural analysis of enzymes can be accomplished at true atomic resolution thus making possible to shed light on otherwise concealed fine-structural traits of bound substrates, intermediates, cofactors and protein groups. We highlight recent structural studies of enzymes using ultrahigh-resolution X-ray protein crystallography showcasing its enormous potential as a tool in the elucidation of enzymatic mechanisms and in unveiling fundamental principles of enzyme catalysis. We discuss the observation of seemingly hyper-reactive, physically distorted cofactors and intermediates with elongated scissile substrate bonds, the detection of 'hidden' conformational and chemical equilibria and the analysis of protonation states with surprising findings. In delicate cases, atomic resolution is required to unambiguously disclose the identity of atoms as demonstrated for the metal cluster in nitrogenase. In addition to the pivotal structural findings and the implications for our understanding of enzyme catalysis, we further provide a practical framework for resolution enhancement through optimized data acquisition and processing. Copyright © 2014 Elsevier Ltd. All rights reserved.

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.

MRI of Heterogeneous Hydrogenation Reactions Using Parahydrogen Polarization

Energy Technology Data Exchange (ETDEWEB)

Burt, Scott Russell [Univ. of California, Berkeley, CA (United States)

2008-01-01

The power of magnetic resonance imaging (MRI) is its ability to image the internal structure of optically opaque samples and provide detailed maps of a variety of important parameters, such as density, diffusion, velocity and temperature. However, one of the fundamental limitations of this technique is its inherent low sensitivity. For example, the low signal to noise ratio (SNR) is particularly problematic for imaging gases in porous materials due to the low density of the gas and the large volume occluded by the porous material. This is unfortunate, as many industrially relevant chemical reactions take place at gas-surface interfaces in porous media, such as packed catalyst beds. Because of this severe SNR problem, many techniques have been developed to directly increase the signal strength. These techniques work by manipulating the nuclear spin populations to produce polarized} (i.e., non-equilibrium) states with resulting signal strengths that are orders of magnitude larger than those available at thermal equilibrium. This dissertation is concerned with an extension of a polarization technique based on the properties of parahydrogen. Specifically, I report on the novel use of heterogeneous catalysis to produce parahydrogen induced polarization and applications of this new technique to gas phase MRI and the characterization of micro-reactors. First, I provide an overview of nuclear magnetic resonance (NMR) and how parahydrogen is used to improve the SNR of the NMR signal. I then present experimental results demonstrating that it is possible to use heterogeneous catalysis to produce parahydrogen-induced polarization. These results are extended to imaging void spaces using a parahydrogen polarized gas. In the second half of this dissertation, I demonstrate the use of parahydrogen-polarized gas-phase MRI for characterizing catalytic microreactors. Specifically, I show how the improved SNR allows one to map parameters important for characterizing the heat and mass

Acquisition of an X-Ray Diffractometer with WAXS and SAXS for Materials Research

Science.gov (United States)

2015-03-31

radiation element detection, (ii) as adsorbents for organic and heavy metal contaminants, and, (iii) heterogeneous catalysis for degradation of...conformation of diffraction patterns from 25°C to 120°C. (ii) MOFs as adsorbents for organics and heavy metals : MOFs are well known for their various...applications in the field of adsorption and separation. MOF-235 is an iron-terephthalate metal -organic framework composed of non-toxic Fe3O clusters

Green's Function and Stress Fields in Stochastic Heterogeneous Continua

Science.gov (United States)

Negi, Vineet

Many engineering materials used today are heterogenous in composition e.g. Composites - Polymer Matrix Composites, Metal Matrix Composites. Even, conventional engineering materials - metals, plastics, alloys etc. - may develop heterogeneities, like inclusions and residual stresses, during the manufacturing process. Moreover, these materials may also have intrinsic heterogeneities at a nanoscale in the form of grain boundaries in metals, crystallinity in amorphous polymers etc. While, the homogenized constitutive models for these materials may be satisfactory at a macroscale, recent studies of phenomena like fatigue failure, void nucleation, size-dependent brittle-ductile transition in polymeric nanofibers reveal a major play of micro/nanoscale physics in these phenomena. At this scale, heterogeneities in a material may no longer be ignored. Thus, this demands a study into the effects of various material heterogeneities. In this work, spatial heterogeneities in two material properties - elastic modulus and yield stress - have been investigated separately. The heterogeneity in the elastic modulus is studied in the context of Green's function. The Stochastic Finite Element method is adopted to get the mean statistics of the Green's function defined on a stochastic heterogeneous 2D infinite space. A study of the elastic-plastic transition in a domain having stochastic heterogenous yield stress was done using Mont-Carlo methods. The statistics for various stress and strain fields during the transition were obtained. Further, the effects of size of the domain and the strain-hardening rate on the stress fields during the heterogeneous elastic-plastic transition were investigated. Finally, a case is made for the role of the heterogenous elastic-plastic transition in damage nucleation and growth.

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

Science.gov (United States)

Serna, Pedro; Gates, Bruce C

2014-08-19

Recent advances in the synthesis and characterization of small, essentially molecular metal complexes and metal clusters on support surfaces have brought new insights to catalysis and point the way to systematic catalyst design. We summarize recent work unraveling effects of key design variables of site-isolated catalysts: the metal, metal nuclearity, support, and other ligands on the metals, also considering catalysts with separate, complementary functions on supports. The catalysts were synthesized with the goal of structural simplicity and uniformity to facilitate incisive characterization. Thus, they are essentially molecular species bonded to porous supports chosen for their high degree of uniformity; the supports are crystalline aluminosilicates (zeolites) and MgO. The catalytic species are synthesized in reactions of organometallic precursors with the support surfaces; the precursors include M(L)2(acetylacetonate)1-2, with M = Ru, Rh, Ir, or Au and the ligands L = C2H4, CO, or CH3. Os3(CO)12 and Ir4(CO)12 are used as precursors of supported metal clusters, and some such catalysts are made by ship-in-a-bottle syntheses to trap the clusters in zeolite cages. The simplicity and uniformity of the supported catalysts facilitate precise structure determinations, even in reactive atmospheres and during catalysis. The methods of characterizing catalysts in reactive atmospheres include infrared (IR), extended X-ray absorption fine structure (EXAFS), X-ray absorption near edge structure (XANES), and nuclear magnetic resonance (NMR) spectroscopies, and complementary methods include density functional theory and atomic-resolution aberration-corrected scanning transmission electron microscopy for imaging of individual metal atoms. IR, NMR, XANES, and microscopy data demonstrate the high degrees of uniformity of well-prepared supported species. The characterizations determine the compositions of surface metal complexes and clusters, including the ligands and the metal

Heterogeneous catalysis : introduction

NARCIS (Netherlands)

Niemantsverdriet, J.W.; Schlögl, R.; Reedijk, J.; Poeppelmeier, K.

2013-01-01

Comprehensive Inorganic Chemistry II reviews and examines topics of relevance to today’s inorganic chemists. Covering more interdisciplinary and high impact areas, Comprehensive Inorganic Chemistry II includes biological inorganic chemistry, solid state chemistry, materials chemistry, and

Study of dosimetric effects due to metallic heterogeneity of tissue expanders in post-mastectomy radiotherapy

International Nuclear Information System (INIS)

Trombetta, Debora M.; Silva, Ademir X. da; Rosa, Luiz A.R. da

2009-01-01

Breast cancer is the most common cancer among women. In each year approximately 20% of the new cases of cancer in women are breast cancers. Despite the increase in the use of breast-conserving treatment, some women still require mastectomy as their primary surgical management. A large part of these women, whom undergo a mastectomy, realize a breast reconstruction afterwards. The most common options for reconstruction include autogenous tissue techniques and tissue expansion followed by breast implant placement. Many trials have demonstrated a survival benefit associated with post-mastectomy radiotherapy mainly if the treatment starts right after the mastectomy. In such case patients whom were realizing the breast reconstruction using tissue expanders can be irradiated using this. These patients posses a material with high atomic number within the irradiated area, so this metallic port becomes an heterogeneity which can modify the calculated doses distribution for the treatment. The study was due through the quantification of the relative transmission of 6MV and 15MV radiotherapy beam, making use of computer simulations with Monte Carlo method implemented by the MCNPX code. The results show that the presence of this metallic heterogeneity changes the transmission of the beam, causing a reduction up to 13% in the geometric shadowed region. According to dosimetric protocols, which recommend that the reduction in the dose should be bellow of 5%, the difference found in the study could be significant. (author)

Metal-adeninate vertices for the construction of an exceptionally porous metal-organic framework.

Science.gov (United States)

An, Jihyun; Farha, Omar K; Hupp, Joseph T; Pohl, Ehmke; Yeh, Joanne I; Rosi, Nathaniel L

2012-01-03

Metal-organic frameworks comprising metal-carboxylate cluster vertices and long, branched organic linkers are the most porous materials known, and therefore have attracted tremendous attention for many applications, including gas storage, separations, catalysis and drug delivery. To increase metal-organic framework porosity, the size and complexity of linkers has increased. Here we present a promising alternative strategy for constructing mesoporous metal-organic frameworks that addresses the size of the vertex rather than the length of the organic linker. This approach uses large metal-biomolecule clusters, in particular zinc-adeninate building units, as vertices to construct bio-MOF-100, an exclusively mesoporous metal-organic framework. Bio-MOF-100 exhibits a high surface area (4,300 m(2) g(-1)), one of the lowest crystal densities (0.302 g cm(-3)) and the largest metal-organic framework pore volume reported to date (4.3 cm(3) g(-1)).

Catalysis as an important tool of green chemistry

Energy Technology Data Exchange (ETDEWEB)

Beletskaya, Irina P [Department of Chemistry, M.V. Lomonosov Moscow State University, Moscow (Russian Federation); Kustov, Leonid M [N.D.Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow (Russian Federation)

2010-08-12

Published data of the last decade demonstrating the significant achievements in the catalytic synthesis of organic compounds are analyzed from the green chemistry standpoint. It is demonstrated that the use of new catalysts (including nano-sized ones) and solvents (water, ionic liquids, fluorinated derivatives), microwave processes, superctitical and two-phase media, and heterogenized metal complex catalytic systems should be distinguished among the most promising approaches to such processes. The main applications of metal complex systems are considered, in particular, hydrogenation, partial oxidation and cross-coupling reactions, in particular, enantioselective reactions.

Catalysis as an important tool of green chemistry

International Nuclear Information System (INIS)

Beletskaya, Irina P; Kustov, Leonid M

2010-01-01

Published data of the last decade demonstrating the significant achievements in the catalytic synthesis of organic compounds are analyzed from the green chemistry standpoint. It is demonstrated that the use of new catalysts (including nano-sized ones) and solvents (water, ionic liquids, fluorinated derivatives), microwave processes, superctitical and two-phase media, and heterogenized metal complex catalytic systems should be distinguished among the most promising approaches to such processes. The main applications of metal complex systems are considered, in particular, hydrogenation, partial oxidation and cross-coupling reactions, in particular, enantioselective reactions.

Synthesis of a molecularly defined single-active site heterogeneous catalyst for selective oxidation of N-heterocycles.

Science.gov (United States)

Zhang, Yujing; Pang, Shaofeng; Wei, Zhihong; Jiao, Haijun; Dai, Xingchao; Wang, Hongli; Shi, Feng

2018-04-13

Generally, a homogeneous catalyst exhibits good activity and defined active sites but it is difficult to recycle. Meanwhile, a heterogeneous catalyst can easily be reused but its active site is difficult to reveal. It is interesting to bridge the gap between homogeneous and heterogeneous catalysis via controllable construction of a heterogeneous catalyst containing defined active sites. Here, we report that a molecularly defined, single-active site heterogeneous catalyst has been designed and prepared via the oxidative polymerization of maleimide derivatives. These polymaleimide derivatives can be active catalysts for the selective oxidation of heterocyclic compounds to quinoline and indole via the recycling of -C=O and -C-OH groups, which was confirmed by tracing the reaction with GC-MS using maleimide as the catalyst and by FT-IR analysis with polymaleimide as the catalyst. These results might promote the development of heterogeneous catalysts with molecularly defined single active sites exhibiting a comparable activity to homogeneous catalysts.

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.

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.

Scalable synthesis and post-modification of a mesoporous metal-organic framework called NU-1000.

Science.gov (United States)

Wang, Timothy C; Vermeulen, Nicolaas A; Kim, In Soo; Martinson, Alex B F; Stoddart, J Fraser; Hupp, Joseph T; Farha, Omar K

2016-01-01

The synthesis of NU-1000, a highly robust mesoporous (containing pores >2 nm) metal-organic framework (MOF), can be conducted efficiently on a multigram scale from inexpensive starting materials. Tetrabromopyrene and (4-(ethoxycarbonyl)phenyl)boronic acid can easily be coupled to prepare the requisite organic strut with four metal-binding sites in the form of four carboxylic acids, while zirconyl chloride octahydrate is used as a precursor for the well-defined metal oxide clusters. NU-1000 has been reported as an excellent candidate for the separation of gases, and it is a versatile scaffold for heterogeneous catalysis. In particular, it is ideal for the catalytic deactivation of nerve agents, and it shows great promise as a new generic platform for a wide range of applications. Multiple post-synthetic modification protocols have been developed using NU-1000 as the parent material, making it a potentially useful scaffold for several catalytic applications. The procedure for the preparation of NU-1000 can be scaled up reliably, and it is suitable for the production of 50 g of the tetracarboxylic acid containing organic linker and 200 mg-2.5 g of NU-1000. The entire synthesis is performed without purification by column chromatography and can be completed within 10 d.

Metal-Free Approaches to Sterically-Hindered Bonds

Science.gov (United States)

Dunham, Veronica Vin-yi

Developing methods to perform cross coupling reactions by means of catalysis is highly desirable in chemistry. Many industries in today's society, such as the petroleum, agriculture, pharmaceutical, electronics, and polymer industry, use catalysis to some extent whether it is to make molecules that offer crop protection or toward the synthesis of the active ingredient of a medication. It is noteworthy that over 90% of chemicals are made through catalytic processes and that the catalyst market reached $17 billion in 2014, which demonstrates the demand for such methods. While transition metal catalysts have advantages such as low catalyst loading, broad reactivity, and that they have been well studied, some disadvantages are that they can be relatively expensive and sometimes air sensitive which can make them challenging to use. Organocatalysis, specifically noncovalent catalysis operating through hydrogen bond donating interactions, offers an environmentally-friendly alternative to transition metal catalysis. Our lab utilizes organocatalysis as a strategy to synthesize challenging, sterically-hindered bonds. Nitrimines have been identified as powerful coupling partners for the sustainable construction of new sterically congested carbon-carbon and carbon-heteroatom bonds. Using urea catalysis, a metal-free method to synthesize previously inaccessible enamines has been developed. Conventional routes to synthesize enamines as important building blocks toward target molecules generally require Lewis/Bronsted acids or expensive transition metals; however, these methods are often unsuccessful when stericallyhindered substrates are used. To address this synthetic challenge, it was hypothesized that hydrogen bonding interactions between a urea organocatalyst and nitrimine would generate a reactive species suited for the effective carbon-nitrogen coupling with amines to give the desired enamine products. This reaction provides high yields (up to 99%) of enamines using a

Pore-Confined Light Metal Hydrides for Energy Storage and Catalysis

NARCIS (Netherlands)

Bramwell, P.L.|info:eu-repo/dai/nl/371685117

2017-01-01

Light metal hydrides have enjoyed several decades of attention in the field of hydrogen storage, but their applications have recently begun to diversify more and more into the broader field of energy storage. For example, light metal hydrides have shown great promise as battery materials, in sensors

Graphene-Based Nanomaterials as Heterogeneous Acid Catalysts: A Comprehensive Perspective

Directory of Open Access Journals (Sweden)

Bhaskar Garg

2014-09-01

Full Text Available Acid catalysis is quite prevalent and probably one of the most routine operations in both industrial processes and research laboratories worldwide. Recently, “graphene”, a two dimensional single-layer carbon sheet with hexagonal packed lattice structure, imitative of nanomaterials, has shown great potential as alternative and eco-friendly solid carbocatalyst for a variety of acid-catalyzed reactions. Owing to their exceptional physical, chemical, and mechanical properties, graphene-based nanomaterials (G-NMs offer highly stable Brønsted acidic sites, high mass transfer, relatively large surface areas, water tolerant character, and convenient recoverability as well as recyclability, whilst retaining high activity in acid-catalyzed chemical reactions. This comprehensive review focuses on the chemistry of G-NMs, including their synthesis, characterization, properties, functionalization, and up-to-date applications in heterogeneous acid catalysis. In line with this, in certain instances readers may find herein some criticisms that should be taken as constructive and would be of value in understanding the scope and limitations of current approaches utilizing graphene and its derivatives for the same.

Understanding the effect of steps, strain, poisons, and alloying: Methane activation on Ni surfaces

DEFF Research Database (Denmark)

Abild-Pedersen, Frank; Greeley, Jeffrey Philip; Nørskov, Jens Kehlet

2005-01-01

It is shown that a single parameter characterizing the electronic structure of a transition metal surface, the d-band center (epsilon(d)), can be used to provide a unified description of a range of phenomena in heterogeneous catalysis. Using methane activation on Ni surfaces as an example, we show...

Surface/structure functionalization of copper-based catalysts by metal-support and/or metal–metal interactions

Energy Technology Data Exchange (ETDEWEB)

Konsolakis, Michalis, E-mail: mkonsol@science.tuc.gr [School of Production Engineering and Management, Technical University of Crete, GR-73100 Chania, Crete (Greece); Ioakeimidis, Zisis [Department of Mechanical Engineering, University of Western Macedonia, Bakola and Sialvera, GR-50100 Kozani (Greece)

2014-11-30

Highlights: • The surface chemistry of Cu-based catalysts is adjusted by metal-support or metal–metal interactions. • Three series of catalysts, i.e., Cu/REOs, Cu/Ce{sub 1−x}Sm{sub x}O{sub δ} and Cu–Co/CeO{sub 2} were prepared. • The local structure of Cu sites is remarkably affected by support or active phase modification. • Useful insights toward the fundamental understanding of Cu-catalyzed reactions are provided. - Abstract: Cu-based catalysts have recently attracted great attention both in catalysis and electro-catalysis fields due to their excellent catalytic performance and low cost. Given that their performance is determined, to a great extent, by Cu sites local environment, considerable efforts have been devoted on the strategic modifications of the electronic and structural properties of Cu sites. In this regard, the feasibility of tuning the local structure of Cu entities by means of metal-support or metal–metal interactions is investigated. More specifically, the physicochemical properties of Cu entities are modified by employing: (i) different oxides (CeO{sub 2}, La{sub 2}O{sub 3}, Sm{sub 2}O{sub 3}), or (ii) ceria-based mixed oxides (Ce{sub 1−x}Sm{sub x}O{sub δ}) as supporting carriers, and (iii) a second metal (Cobalt) adjacent to Cu (bimetallic Cu–Co/CeO{sub 2}). A characterization study, involving BET, XRD, TPR, and XPS, reveal that significant modifications on structural, redox and electronic properties of Cu sites can be induced by adopting either different oxide carriers or bimetallic complexes. Fundamental insights into the tuning of Cu local environment by metal-support or metal–metal interactions are provided, paving the way for real-life industrial applications.

CHROTRAN 1.0. A mathematical and computational model for in situ heavy metal remediation in heterogeneous aquifers

Energy Technology Data Exchange (ETDEWEB)

Hansen, Scott K.; Pandey, Sachin; Karra, Satish; Vesselinov, Velimir V. [Los Alamos National Laboratory, Los Alamos, NM (United States). Computational Earth Science Group (EES-16)

2017-07-01

Groundwater contamination by heavy metals is a critical environmental problem for which in situ remediation is frequently the only viable treatment option. For such interventions, a multi-dimensional reactive transport model of relevant biogeochemical processes is invaluable. To this end, we developed a model, chrotran, for in situ treatment, which includes full dynamics for five species: a heavy metal to be remediated, an electron donor, biomass, a nontoxic conservative bio-inhibitor, and a biocide. Direct abiotic reduction by donor-metal interaction as well as donor-driven biomass growth and bio-reduction are modeled, along with crucial processes such as donor sorption, bio-fouling, and biomass death. Our software implementation handles heterogeneous flow fields, as well as arbitrarily many chemical species and amendment injection points, and features full coupling between flow and reactive transport. We describe installation and usage and present two example simulations demonstrating its unique capabilities. One simulation suggests an unorthodox approach to remediation of Cr(VI) contamination.

CHROTRAN 1.0: A mathematical and computational model for in situ heavy metal remediation in heterogeneous aquifers

Science.gov (United States)

Hansen, Scott K.; Pandey, Sachin; Karra, Satish; Vesselinov, Velimir V.

2017-12-01

Groundwater contamination by heavy metals is a critical environmental problem for which in situ remediation is frequently the only viable treatment option. For such interventions, a multi-dimensional reactive transport model of relevant biogeochemical processes is invaluable. To this end, we developed a model, chrotran, for in situ treatment, which includes full dynamics for five species: a heavy metal to be remediated, an electron donor, biomass, a nontoxic conservative bio-inhibitor, and a biocide. Direct abiotic reduction by donor-metal interaction as well as donor-driven biomass growth and bio-reduction are modeled, along with crucial processes such as donor sorption, bio-fouling, and biomass death. Our software implementation handles heterogeneous flow fields, as well as arbitrarily many chemical species and amendment injection points, and features full coupling between flow and reactive transport. We describe installation and usage and present two example simulations demonstrating its unique capabilities. One simulation suggests an unorthodox approach to remediation of Cr(VI) contamination.

CHROTRAN 1.0. A mathematical and computational model for in situ heavy metal remediation in heterogeneous aquifers

International Nuclear Information System (INIS)

Hansen, Scott K.; Pandey, Sachin; Karra, Satish; Vesselinov, Velimir V.

2017-01-01

Groundwater contamination by heavy metals is a critical environmental problem for which in situ remediation is frequently the only viable treatment option. For such interventions, a multi-dimensional reactive transport model of relevant biogeochemical processes is invaluable. To this end, we developed a model, chrotran, for in situ treatment, which includes full dynamics for five species: a heavy metal to be remediated, an electron donor, biomass, a nontoxic conservative bio-inhibitor, and a biocide. Direct abiotic reduction by donor-metal interaction as well as donor-driven biomass growth and bio-reduction are modeled, along with crucial processes such as donor sorption, bio-fouling, and biomass death. Our software implementation handles heterogeneous flow fields, as well as arbitrarily many chemical species and amendment injection points, and features full coupling between flow and reactive transport. We describe installation and usage and present two example simulations demonstrating its unique capabilities. One simulation suggests an unorthodox approach to remediation of Cr(VI) contamination.

CHROTRAN 1.0: A mathematical and computational model for in situ heavy metal remediation in heterogeneous aquifers

Directory of Open Access Journals (Sweden)

S. K. Hansen

2017-12-01

Full Text Available Groundwater contamination by heavy metals is a critical environmental problem for which in situ remediation is frequently the only viable treatment option. For such interventions, a multi-dimensional reactive transport model of relevant biogeochemical processes is invaluable. To this end, we developed a model, chrotran, for in situ treatment, which includes full dynamics for five species: a heavy metal to be remediated, an electron donor, biomass, a nontoxic conservative bio-inhibitor, and a biocide. Direct abiotic reduction by donor–metal interaction as well as donor-driven biomass growth and bio-reduction are modeled, along with crucial processes such as donor sorption, bio-fouling, and biomass death. Our software implementation handles heterogeneous flow fields, as well as arbitrarily many chemical species and amendment injection points, and features full coupling between flow and reactive transport. We describe installation and usage and present two example simulations demonstrating its unique capabilities. One simulation suggests an unorthodox approach to remediation of Cr(VI contamination.

Development of a heterogeneous catalyst for lignocellulosic biomass conversion : glucose dehydration by metal chlorides in a silica-supported ionic liquid layer

NARCIS (Netherlands)

Degirmenci, V.; Hensen, E.J.M.

2014-01-01

An attempt is made to immobilize the homogeneous metal chloride/EMIMCl catalyst for glucose dehydration to 5-hydroxymethylfurfural. To this end, ionic liquid fragments were grafted to the surface of SBA-15 to generate a heterogenized mimick of the homogeneous reaction medium. Despite a decrease in

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...

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.

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...

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....

Photocatalytic carbon dioxide reduction with rhodium-based catalysts in solution and heterogenized within metal-organic frameworks.

Science.gov (United States)

Chambers, Matthew B; Wang, Xia; Elgrishi, Noémie; Hendon, Christopher H; Walsh, Aron; Bonnefoy, Jonathan; Canivet, Jérôme; Quadrelli, Elsje Alessandra; Farrusseng, David; Mellot-Draznieks, Caroline; Fontecave, Marc

2015-02-01

The first photosensitization of a rhodium-based catalytic system for CO2 reduction is reported, with formate as the sole carbon-containing product. Formate has wide industrial applications and is seen as valuable within fuel cell technologies as well as an interesting H2 -storage compound. Heterogenization of molecular rhodium catalysts is accomplished via the synthesis, post-synthetic linker exchange, and characterization of a new metal-organic framework (MOF) Cp*Rh@UiO-67. While the catalytic activities of the homogeneous and heterogeneous systems are found to be comparable, the MOF-based system is more stable and selective. Furthermore it can be recycled without loss of activity. For formate production, an optimal catalyst loading of ∼10 % molar Rh incorporation is determined. Increased incorporation of rhodium catalyst favors thermal decomposition of formate into H2 . There is no precedent for a MOF catalyzing the latter reaction so far. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Treatment of heterogeneous mixed wastes: Enzyme degradation of cellulosic materials contaminated with hazardous organics and toxic and radioactive metals

International Nuclear Information System (INIS)

Vanderberg, L.A.; Foreman, T.M.; Attrep, M. Jr.; Brainard, J.R.; Sauer, N.

1999-01-01

The redirection and downsizing of the US Department of Energy's nuclear weapons complex requires that many facilities be decontaminated and decommissioned (D and D). At Los Alamos National Laboratory, much of the low-level radioactive, mixed, and hazardous/chemical waste volume handled by waste management operations was produced by D and D and environmental restoration activities. A combination of technologies--air stripping and biodegradation of volatile organics, enzymatic digestion of cellulosics, and metal ion extraction--was effective in treating a radiologically contaminated heterogeneous paint-stripping waste. Treatment of VOCs using a modified bioreactor avoided radioactive contamination of byproduct biomass and inhibition of biodegradation by toxic metal ions in the waste. Cellulase digestion of bulk cellulose minimized the final solid waste volume by 80%. Moreover, the residue passed TCLP for RCRA metals. Hazardous metals and radioactivity in byproduct sugar solutions were removed using polymer filtration, which employs a combination of water-soluble chelating polymers and ultrafiltration to separate and concentrate metal contaminants. Polymer filtration was used to concentrate RCRA metals and radioactivity into <5% of the original wastewater volume. Permeate solutions had no detectable radioactivity and were below RCRA-allowable discharge limits for Pb and Cr

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

Use of Heterogenized Metal Complexes in Hydrogenation Reactions: Comparison of Hydrogenation and CTH Reactions.

Czech Academy of Sciences Publication Activity Database

Bata, P.; Zsigmond, A.; Gyémánt, M.; Czeglédi, A.; Klusoň, Petr

2015-01-01

Roč. 41, č. 12 (2015), s. 9281-9294 ISSN 0922-6168. [Pannonian Symposium on Catalysis /12./. Castle Trest, 16.09.2014-20.09.2014] Institutional support: RVO:67985858 Keywords : catalytic transfer hydrogenation * iron-phthalocyanine catalyst * chemoselectivity Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 1.833, year: 2015

A New Class of Metal-Cyclam-Based Zirconium Metal–Organic Frameworks for CO ₂ Adsorption and Chemical Fixation

Energy Technology Data Exchange (ETDEWEB)

Zhu, Jie [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States). Dept. of Chemistry; Usov, Pavel M. [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States). Dept. of Chemistry; Xu, Wenqian [Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS) and X-ray Science Division; Celis-Salazar, Paula J. [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States). Dept. of Chemistry; Lin, Shaoyang [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States). Dept. of Chemistry; Kessinger, Matthew C. [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States). Dept. of Chemistry; Landaverde-Alvarado, Carlos [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States). Dept. of Chemical Engineering and Macromolecules Innovation Inst.; Cai, Meng [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States). Dept. of Chemistry; May, Ann M. [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States). Dept. of Chemistry; Slebodnick, Carla [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States). Dept. of Chemistry; Zhu, Dunru [Nanjing Univ. of Technology (China). State Key Lab. of Materials-Oriented Chemical Engineering (MCE) and College of Chemical Engineering; Senanayake, Sanjaya D. [Brookhaven National Lab. (BNL), Upton, NY (United States). Dept. of Chemistry; Morris, Amanda J. [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States). Dept. of Chemistry and Macromolecules Innovation Inst.

2017-12-22

Metal-organic frameworks (MOFs) have shown great promise in catalysis, mainly due to their high content of active centers, large internal surface areas, tunable pore size, and versatile chemical functionalities. However, it is a challenge to rationally design and construct MOFs that can serve as highly stable and reusable heterogeneous catalysts. Here two new robust 3D porous metal-cyclam-based zirconium MOFs, denoted VPI-100 (Cu) and VPI-100 (Ni), have been prepared by a modulated synthetic strategy. The frameworks are assembled by eight-connected Zr-6 clusters and metallocyclams as organic linkers. Importantly, the cyclam core has accessible axial coordination sites for guest interactions and maintains the electronic properties exhibited by the parent cyclam ring. The VPI-100 MOFs exhibit excellent chemical stability in various organic and aqueous solvents over a wide pH range and show high CO2 uptake capacity (up to similar to 9.83 wt% adsorption at 273 K under 1 atm). Moreover, VPI-100 MOFs demonstrate some of the highest reported catalytic activity values (turnover frequency and conversion efficiency) among Zr-based MOFs for the chemical fixation of CO2 with epoxides, including sterically hindered epoxides. The MOFs, which bear dual catalytic sites (Zr and Cu/Ni), enable chemistry not possible with the cyclam ligand under the same conditions and can be used as recoverable stable heterogeneous catalysts without losing performance.

Engineering Single-Atom Cobalt Catalysts toward Improved Electrocatalysis.

Science.gov (United States)

Wan, Gang; Yu, Pengfei; Chen, Hangrong; Wen, Jianguo; Sun, Cheng-Jun; Zhou, Hua; Zhang, Nian; Li, Qianru; Zhao, Wanpeng; Xie, Bing; Li, Tao; Shi, Jianlin

2018-04-01

The development of cost-effective catalysts to replace noble metal is attracting increasing interests in many fields of catalysis and energy, and intensive efforts are focused on the integration of transition-metal sites in carbon as noble-metal-free candidates. Recently, the discovery of single-atom dispersed catalyst (SAC) provides a new frontier in heterogeneous catalysis. However, the electrocatalytic application of SAC is still subject to several theoretical and experimental limitations. Further advances depend on a better design of SAC through optimizing its interaction with adsorbates during catalysis. Here, distinctive from previous studies, favorable 3d electronic occupation and enhanced metal-adsorbates interactions in single-atom centers via the construction of nonplanar coordination is achieved, which is confirmed by advanced X-ray spectroscopic and electrochemical studies. The as-designed atomically dispersed cobalt sites within nonplanar coordination show significantly improved catalytic activity and selectivity toward the oxygen reduction reaction, approaching the benchmark Pt-based catalysts. More importantly, the illustration of the active sites in SAC indicates metal-natured catalytic sites and a media-dependent catalytic pathway. Achieving structural and electronic engineering on SAC that promotes its catalytic performances provides a paradigm to bridge the gap between single-atom catalysts design and electrocatalytic applications. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Porous-Hybrid Polymers as Platforms for Heterogeneous Photochemical Catalysis

KAUST Repository

Haikal, Rana R.

2016-07-18

A number of permanently porous polymers containing Ru(bpy)n photosensitizer or a cobaloxime complex, as a proton-reduction catalyst, were constructed via one-pot Sonogashira-Hagihara (SH) cross-coupling reactions. This process required minimal workup to access porous platforms with control over the apparent surface area, pore volume, and chemical functionality from suitable molecular building blocks (MBBs) containing the Ru or Co complexes, as rigid and multi-topic nodes. The cobaloxime molecular building block, generated through in situ metalation, afforded a microporous solid that demonstrated noticeable catalytic activity towards hydrogen-evolution reaction (HER) with remarkable recyclability. We further demonstrated, in two cases, the ability to affect the excited state lifetime of the covalently-immobilized Ru(bpy)3 complex attained through deliberate utilization of the organic linkers of variable dimensions. Overall, this approach facilitates construction of tunable porous solids, with hybrid composition and pronounced chemical and physical stability, based on the well-known Ru(bpy)nor the cobaloxime complexes.

Porous-Hybrid Polymers as Platforms for Heterogeneous Photochemical Catalysis

KAUST Repository

Haikal, Rana R.; Wang, Xia; Hassan, Youssef S.; Parida, Manas R.; Banavoth, Murali; Mohammed, Omar F.; Pellechia, Perry J.; Fontecave, Marc; Alkordi, Mohamed H.

2016-01-01

A number of permanently porous polymers containing Ru(bpy)n photosensitizer or a cobaloxime complex, as a proton-reduction catalyst, were constructed via one-pot Sonogashira-Hagihara (SH) cross-coupling reactions. This process required minimal workup to access porous platforms with control over the apparent surface area, pore volume, and chemical functionality from suitable molecular building blocks (MBBs) containing the Ru or Co complexes, as rigid and multi-topic nodes. The cobaloxime molecular building block, generated through in situ metalation, afforded a microporous solid that demonstrated noticeable catalytic activity towards hydrogen-evolution reaction (HER) with remarkable recyclability. We further demonstrated, in two cases, the ability to affect the excited state lifetime of the covalently-immobilized Ru(bpy)3 complex attained through deliberate utilization of the organic linkers of variable dimensions. Overall, this approach facilitates construction of tunable porous solids, with hybrid composition and pronounced chemical and physical stability, based on the well-known Ru(bpy)nor the cobaloxime complexes.

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…

Structural and catalytic effects of an invariant purine substitution in the hammerhead ribozyme: implications for the mechanism of acid–base catalysis

Science.gov (United States)

Schultz, Eric P.; Vasquez, Ernesto E.; Scott, William G.

2014-01-01

The hammerhead ribozyme catalyzes RNA cleavage via acid–base catalysis. Whether it does so by general acid–base catalysis, in which the RNA itself donates and abstracts protons in the transition state, as is typically assumed, or by specific acid–base catalysis, in which the RNA plays a structural role and proton transfer is mediated by active-site water molecules, is unknown. Previous biochemical and crystallographic experiments implicate an invariant purine in the active site, G12, as the general base. However, G12 may play a structural role consistent with specific base catalysis. To better understand the role of G12 in the mechanism of hammerhead catalysis, a 2.2 Å resolution crystal structure of a hammerhead ribozyme from Schistosoma mansoni with a purine substituted for G12 in the active site of the ribozyme was obtained. Comparison of this structure (PDB entry 3zd4), in which A12 is substituted for G, with three previously determined structures that now serve as important experimental controls, allows the identification of structural perturbations that are owing to the purine substitution itself. Kinetic measurements for G12 purine-substituted schistosomal hammerheads confirm a previously observed dependence of rate on the pK a of the substituted purine; in both cases inosine, which is similar to G in pK a and hydrogen-bonding properties, is unexpectedly inactive. Structural comparisons indicate that this may primarily be owing to the lack of the exocyclic 2-amino group in the G12A and G12I substitutions and its structural effect upon both the nucleotide base and phosphate of A9. The latter involves the perturbation of a previously identified and well characterized metal ion-binding site known to be catalytically important in both minimal and full-length hammerhead ribozyme sequences. The results permit it to be suggested that G12 plays an important role in stabilizing the active-site structure. This result, although not inconsistent with the

Structural and catalytic effects of an invariant purine substitution in the hammerhead ribozyme: implications for the mechanism of acid-base catalysis.

Science.gov (United States)

Schultz, Eric P; Vasquez, Ernesto E; Scott, William G

2014-09-01

The hammerhead ribozyme catalyzes RNA cleavage via acid-base catalysis. Whether it does so by general acid-base catalysis, in which the RNA itself donates and abstracts protons in the transition state, as is typically assumed, or by specific acid-base catalysis, in which the RNA plays a structural role and proton transfer is mediated by active-site water molecules, is unknown. Previous biochemical and crystallographic experiments implicate an invariant purine in the active site, G12, as the general base. However, G12 may play a structural role consistent with specific base catalysis. To better understand the role of G12 in the mechanism of hammerhead catalysis, a 2.2 Å resolution crystal structure of a hammerhead ribozyme from Schistosoma mansoni with a purine substituted for G12 in the active site of the ribozyme was obtained. Comparison of this structure (PDB entry 3zd4), in which A12 is substituted for G, with three previously determined structures that now serve as important experimental controls, allows the identification of structural perturbations that are owing to the purine substitution itself. Kinetic measurements for G12 purine-substituted schistosomal hammerheads confirm a previously observed dependence of rate on the pK(a) of the substituted purine; in both cases inosine, which is similar to G in pK(a) and hydrogen-bonding properties, is unexpectedly inactive. Structural comparisons indicate that this may primarily be owing to the lack of the exocyclic 2-amino group in the G12A and G12I substitutions and its structural effect upon both the nucleotide base and phosphate of A9. The latter involves the perturbation of a previously identified and well characterized metal ion-binding site known to be catalytically important in both minimal and full-length hammerhead ribozyme sequences. The results permit it to be suggested that G12 plays an important role in stabilizing the active-site structure. This result, although not inconsistent with the potential

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.

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

DOE Award No. FG02-93ER14331 Final Technical Report

Energy Technology Data Exchange (ETDEWEB)

Bartynski, Robert [Rutgers Univ., New Brunswick, NJ (United States)

2017-04-02

We have studyed new aspects of the relationships between nanoscale surface features and heterogeneous catalysis or electrocatalysis. We concentrate on atomically rough and morphologically unstable surfaces of catalytic metal single crystals (Re, Ru, Ir) that undergo nanoscale faceting when interacting with strongly adsorbed species (e.g. O, N, C) at elevated temperatures.

Gold nanoparticles on OMS-2 for heterogeneously catalyzed aerobic oxidative α,β-dehydrogenation of β-heteroatom-substituted ketones.

Science.gov (United States)

Yoshii, Daichi; Jin, Xiongjie; Yatabe, Takafumi; Hasegawa, Jun-Ya; Yamaguchi, Kazuya; Mizuno, Noritaka

2016-12-06

In the presence of Au nanoparticles supported on manganese oxide OMS-2 (Au/OMS-2), various kinds of β-heteroatom-substituted α,β-unsaturated ketones (heteroatom = N, O, S) can be synthesized through α,β-dehydrogenation of the corresponding saturated ketones using O 2 (in air) as the oxidant. The catalysis of Au/OMS-2 is truly heterogeneous, and the catalyst can be reused.

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

First principles study of propene polymerization in Ziegler-Natta heterogeneous catalysis

Energy Technology Data Exchange (ETDEWEB)

Boero, M.; Parrinello, M.; Hueffer, S.; Weiss, H.

2000-01-26

In this work the authors address the problem of isotacticity in a realistic heterogeneous Ziegler-Natta system by means of ab initio molecular dynamics. A previously identified 5-fold catalytic center was selected and examined for its ability to select the appropriate olefin enantioface in the chain growth process. The first steps in the propene polymerization process were studied to determine the energetics of the initial complexation phase for the different stereochemical orientations of the incoming propene. Then the authors analyze the subsequent insertions which represent the crucial issue for the formation of a stereospecific polymer chain, and find that the 5-fold catalytic center possesses a huge degree of stereoselectivity. The role of the agostic interaction was examined which can switch from {alpha} to {beta} and allow, even in the presence of a substrate, process that can lead to chain termination.

Microwave irradiation for the facile synthesis of transition-metal nanoparticles (NPs) in ionic liquids (ILs) from metal-carbonyl precursors and Ru-, Rh-, and Ir-NP/IL dispersions as biphasic liquid-liquid hydrogenation nanocatalysts for cyclohexene.

Science.gov (United States)

Vollmer, Christian; Redel, Engelbert; Abu-Shandi, Khalid; Thomann, Ralf; Manyar, Haresh; Hardacre, Christopher; Janiak, Christoph

2010-03-22

Stable chromium, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, cobalt, rhodium, and iridium metal nanoparticles (M-NPs) have been reproducibly obtained by facile, rapid (3 min), and energy-saving 10 W microwave irradiation (MWI) under an argon atmosphere from their metal-carbonyl precursors [M(x)(CO)(y)] in the ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF(4)]). This MWI synthesis is compared to UV-photolytic (1000 W, 15 min) or conventional thermal decomposition (180-250 degrees C, 6-12 h) of [M(x)(CO)(y)] in ILs. The MWI-obtained nanoparticles have a very small (TED), and dynamic light scattering (DLS)). The ruthenium, rhodium, or iridium nanoparticle/IL dispersions are highly active and easily recyclable catalysts for the biphasic liquid-liquid hydrogenation of cyclohexene to cyclohexane with activities of up to 522 (mol product) (mol Ru)(-1) h(-1) and 884 (mol product) (mol Rh)(-1) h(-1) and give almost quantitative conversion within 2 h at 10 bar H(2) and 90 degrees C. Catalyst poisoning experiments with CS(2) (0.05 equiv per Ru) suggest a heterogeneous surface catalysis of Ru-NPs.

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)

Catalysis under Irradiation in the Presence of Non-Metallic Solids; Catalyse sous irradiation en presence de solides non metalliques; Radiatsionnyj kataliz pri nalichii'nemetallicheskikh tverdykh tel; Radiocatalisis en presencia de solidos no metalicos

Energy Technology Data Exchange (ETDEWEB)

Coekelbergs, R.; Crucq, A.; Decot, J.; Degols, L.; Frennet, A.; Lienard, G.; Timmerman, L. [Laboratoire de Chimie Nucleaire, Institut Interuniversitaire des Sciences Nucleaires et Ecole Royale Militaire, Bruxelles (Belgium)

1963-11-15

Catalytic processes induced by radiation in the presence of non-metallic solids are discussed, attention being given exclusively to the effects associated with modification of the steady state concentration of charge carriers. The effect of such modification on the kinetics and equilibrium of heterogeneous reactions is quantitatively estimated within the framework of the electronic theory of catalysis, due regard being paid to the electronic characteristics of the surface of the solid. In conclusion, the relationship between these phenomena, catalyst activation and transfer of energy, as previously described, is discussed. (author) [French] Les auteurs discutent des processus catalytiques induits par les radiations en presence de solides non metalliques. Ils considerent exclusivement les effets lies a la modification de la concentration stationnaire des porteurs de charge.- L'influence de cette modification sur la cinetique et l'equilibre des reactions heterogenes est evaluee quantitativement dans le cadre de la theorie electronique de la catalyse et en tenant compte de caracteristiques electroniques de la surface du solide. Enfin, ils discutent la relation existant entre ces phenomenes, l'activation des catalyseurs et le transfert d'energie decrits anterieurement. (author) [Spanish] Los autores examinan los procesos cataliticos inducidos por las radiaciones en presencia de solidos no metalicos. Consideran exclusivamente los efectos vinculados con la modificacion de la concentracion estacionaria de los portadores de carga. Sobre la base de la teoria electronica de la catalisis y teniendo en cuenta las caracteristicas electronicas de la superficie del solido, determinan cuantitativamente la influencia de aquella modificacion sobre la cinetica y el equilibrio de las reacciones heterogeneas. Por ultimo, analizan la relacion que existe entre estos fenomenos, la activacion de los catalizadores y la transmision de energia descritas anteriormente. (author) [Russian

Biodiesel production from castor oil using heterogeneous Ni doped ZnO nanocatalyst.

Science.gov (United States)

Baskar, G; Aberna Ebenezer Selvakumari, I; Aiswarya, R

2018-02-01

In the present study, castor oil with high free fatty acid was used for biodiesel production using heterogeneous Ni doped ZnO nanocatalyst. Ni doped ZnO nanocomposite calcinated at 800 °C has shown better catalytic activity. Process parameters on heterogeneous catalysis of castor oil into biodiesel were optimized using conventional and Response Surface Methodology (RSM). RSM was found more accurate in estimating the optimum conditions with higher biodiesel yield (95.20%). The optimum conditions for transesterification was found to be oil to methanol molar ratio of 1:8, catalyst loading 11% (w/w), reaction temperature of 55 °C for 60 min of reaction time by response surface method. The reusability studies showed that the nanocatalyst can be reused efficiently for 3 cycles. Copyright © 2017 Elsevier Ltd. All rights reserved.

Exploration of the catalytic use of alkali metal bases

OpenAIRE

Bao, Wei

2017-01-01

This PhD thesis project was concerned with the use of alkali metal amide Brønsted bases and alkali metal alkoxide Lewis bases in (asymmetric) catalysis. The first chapter deals with formal allylic C(sp3)–H bond activation of aromatic and functionalized alkenes for subsequent C–C and C–H bond formations. The second chapter is focused on C(sp3)–Si bond activation of fluorinated pro-nucleophiles in view of C–C bond formations. In the first chapter, a screening of various metal amides...

Particle-based modeling of heterogeneous chemical kinetics including mass transfer.

Science.gov (United States)

Sengar, A; Kuipers, J A M; van Santen, Rutger A; Padding, J T

2017-08-01

Connecting the macroscopic world of continuous fields to the microscopic world of discrete molecular events is important for understanding several phenomena occurring at physical boundaries of systems. An important example is heterogeneous catalysis, where reactions take place at active surfaces, but the effective reaction rates are determined by transport limitations in the bulk fluid and reaction limitations on the catalyst surface. In this work we study the macro-micro connection in a model heterogeneous catalytic reactor by means of stochastic rotation dynamics. The model is able to resolve the convective and diffusive interplay between participating species, while including adsorption, desorption, and reaction processes on the catalytic surface. Here we apply the simulation methodology to a simple straight microchannel with a catalytic strip. Dimensionless Damkohler numbers are used to comment on the spatial concentration profiles of reactants and products near the catalyst strip and in the bulk. We end the discussion with an outlook on more complicated geometries and increasingly complex reactions.

Particle-based modeling of heterogeneous chemical kinetics including mass transfer

Science.gov (United States)

Sengar, A.; Kuipers, J. A. M.; van Santen, Rutger A.; Padding, J. T.

2017-08-01

Connecting the macroscopic world of continuous fields to the microscopic world of discrete molecular events is important for understanding several phenomena occurring at physical boundaries of systems. An important example is heterogeneous catalysis, where reactions take place at active surfaces, but the effective reaction rates are determined by transport limitations in the bulk fluid and reaction limitations on the catalyst surface. In this work we study the macro-micro connection in a model heterogeneous catalytic reactor by means of stochastic rotation dynamics. The model is able to resolve the convective and diffusive interplay between participating species, while including adsorption, desorption, and reaction processes on the catalytic surface. Here we apply the simulation methodology to a simple straight microchannel with a catalytic strip. Dimensionless Damkohler numbers are used to comment on the spatial concentration profiles of reactants and products near the catalyst strip and in the bulk. We end the discussion with an outlook on more complicated geometries and increasingly complex reactions.

Theory of the reaction dynamics of small molecules on metal surfaces

Energy Technology Data Exchange (ETDEWEB)

Jackson, Bret [Univ. of Massachusetts, Amherst, MA (United States)

2016-09-09

The objective of this project has been to develop realistic theoretical models for gas-surface interactions, with a focus on processes important in heterogeneous catalysis. The dissociative chemisorption of a molecule on a metal is a key step in many catalyzed reactions, and is often the rate-limiting step. We have explored the dissociative chemisorption of H₂, H₂O and CH₄ on a variety of metal surfaces. Most recently, our extensive studies of methane dissociation on Ni and Pt surfaces have fully elucidated its dependence on translational energy, vibrational state and surface temperature, providing the first accurate comparisons with experimental data. We have explored Eley-Rideal and hot atom reactions of H atoms with H- and C-covered metal surfaces. H atom interactions with graphite have also been explored, including both sticking and Eley-Rideal recombination processes. Again, our methods made it possible to explain several experiments studying these reactions. The sticking of atoms on metal surfaces has also been studied. To help elucidate the experiments that study these processes, we examine how the reaction dynamics depend upon the nature of the molecule-metal interaction, as well as experimental variables such as substrate temperature, beam energy, angle of impact, and the internal states of the molecules. Electronic structure methods based on Density Functional Theory are used to compute each molecule-metal potential energy surface. Both time-dependent quantum scattering techniques and quasi-classical methods are used to examine the reaction or scattering dynamics. Much of our effort has been directed towards developing improved quantum methods that can accurately describe reactions, as well as include the effects of substrate temperature (lattice vibration).

Mimicking heme enzymes in the solid state: metal-organic materials with selectively encapsulated heme.

Science.gov (United States)

Larsen, Randy W; Wojtas, Lukasz; Perman, Jason; Musselman, Ronald L; Zaworotko, Michael J; Vetromile, Carissa M

2011-07-13

To carry out essential life processes, nature has had to evolve heme enzymes capable of synthesizing and manipulating complex molecules. These proteins perform a plethora of chemical reactions utilizing a single iron porphyrin active site embedded within an evolutionarily designed protein pocket. We herein report the first class of metal-organic materials (MOMs) that mimic heme enzymes in terms of both structure and reactivity. The MOMzyme-1 class is based upon a prototypal MOM, HKUST-1, into which catalytically active metalloporphyrins are selectively encapsulated in a "ship-in-a-bottle" fashion within one of the three nanoscale cages that exist in HKUST-1. MOMs offer unparalleled levels of permanent porosity and their modular nature affords enormous diversity of structures and properties. The MOMzyme-1 class could therefore represent a new paradigm for heme biomimetic catalysis since it combines the activity of a homogeneous catalyst with the stability and recyclability of heterogeneous catalytic systems within a single material.

In-Plane Multimagnetron Approach

Energy Technology Data Exchange (ETDEWEB)

Johnson, Grant E.; Laskin, Julia

2017-04-01

Nanoparticles (NPs) and sub-nanometer clusters containing controlled amounts of different atoms are of interest for a variety of potential applications including catalysis,1, 2 optics,3, 4 magnetics,5-7 sensors,8, 9 and biotheraputics.10, 11 Alloy NPs may possess enhanced physical and chemical properties compared to single metal species due to the additional interplay between their different elemental components. By reducing the quantity of expensive precious metals in alloy NPs by substituting cheaper base metals, it may also be possible to achieve equivalent or even superior performance to pure noble metal NPs for applications such as heterogeneous catalysis at substantially reduced material costs.12 In addition, alloying of elements that are immiscible in bulk form is possible in NPs because the enthalpy of mixing decreases and becomes negative at small particle sizes.13, 14 As a result, a substantially broader array of alloy species may be generated in the form of NPs and sub-nanometer clusters.

Photoelectron diffraction study of Rh nanoparticles growth on Fe3O4/Pd(111) ultrathin film

International Nuclear Information System (INIS)

Abreu, G. J. P.; Pancotti, A; Lima, L. H. de; Landers, R.; Siervo, A. de

2013-01-01

Metallic nanoparticles (NPs) supported on oxides thin films are commonly used as model catalysts for studies of heterogeneous catalysis. Several 4d and 5d metal NPs (for example, Pd, Pt and Au) grown on alumina, ceria and titania have shown strong metal support interaction (SMSI), for instance the encapsulation of the NPs by the oxide. The SMSI plays an important role in catalysis and is very dependent on the support oxide used. The present work investigates the growth mechanism and atomic structure of Rh NPs supported on epitaxial magnetite Fe 3 O 4 (111) ultrathin films prepared on Pd(111) using the Molecular Beam Epitaxy (MBE) technique. The iron oxide and the Rh NPs were characterized using X-ray photoelectron spectroscopy (XPS), low-energy electron diffraction and photoelectron diffraction (PED). The combined XPS and PED results indicate that Rh NPs are metallic, cover approximately 20 % of the iron oxide surface and show height distribution ranging 3–5 ML (monolayers) with essentially a bulk fcc structure.

Adhesion and Atomic Structures of Gold on Ceria Nanostructures:The Role of Surface Structure and Oxidation State of Ceria Supports

Energy Technology Data Exchange (ETDEWEB)

Lin, Yuyuan [Northwestern University, Evanston; Wu, Zili [ORNL; Wen, Jianguo [Argonne National Laboratory (ANL); Poeppelmeier, Kenneth R [Northwestern University, Evanston; Marks, Laurence D [Northwestern University, Evanston

2015-01-01

Recent advances in heterogeneous catalysis have demonstrated that oxides supports with the same material but different shapes can result in metal catalysts with distinct catalytic properties. The shape-dependent catalysis was not well-understood owing to the lack of direct visualization of the atomic structures at metal-oxide interface. Herein, we utilized aberration-corrected electron microscopy and revealed the atomic structures of gold particles deposited on ceria nanocubes and nanorods with {100} or {111} facets exposed. For the ceria nanocube support, gold nanoparticles have extended atom layers at the metal-support interface. In contrast, regular gold nanoparticles and rafts are present on the ceria nanorod support. After hours of water gas shift reaction, the extended gold atom layers and rafts vanish, which is associated with the decrease of the catalytic activities. By understanding the atomic structures of the support surfaces, metal-support interfaces, and morphologies of the gold particles, a direct structure-property relationship is established.

An unsaturated metal site-promoted approach to construct strongly coupled noble metal/HNb3O8 nanosheets for efficient thermo/photo-catalytic reduction.

Science.gov (United States)

Shen, Lijuan; Xia, Yuzhou; Lin, Sen; Liang, Shijing; Wu, Ling

2017-10-05

Creating two-dimensional (2D) crystal-metal heterostructures with an ultrathin thickness has spurred increasing research endeavors in catalysis because of its fascinating opportunities in tuning the electronic state at the surface and enhancing the chemical reactivity. Here we report a novel and facile Nb 4+ -assisted strategy for the in situ growth of highly dispersed Pd nanoparticles (NPs) on monolayer HNb 3 O 8 nanosheets (HNb 3 O 8 NS) constituting a 2D Pd/HNb 3 O 8 NS heterostructure composite without using extra reducing agents and stabilizing agents. The Pd NP formation is directed via a redox reaction between an oxidative Pd salt precursor (H 2 PdCl 4 ) and reductive unsaturated surface metal (Nb 4+ ) sites induced by light irradiation on monolayer HNb 3 O 8 NS. The periodic arrangement of metal Nb nodes on HNb 3 O 8 NS leads to a homogeneous distribution of Pd NPs. Density functional theory (DFT) calculations reveal that the direct redox reaction between the Nb 4+ and Pd 2+ ions leads to a strong chemical interaction between the formed Pd metal NPs and the monolayer HNb 3 O 8 support. Consequently, the as-obtained Pd/HNb 3 O 8 composite serves as a highly efficient bifunctional catalyst in both heterogeneous thermocatalytic and photocatalytic selective reduction of aromatic nitro compounds in water under ambient conditions. The achieved high activity originates from the unique 2D nanosheet configuration and in situ Pd incorporation, which leads to a large active surface area, strong metal-support interaction and enhanced charge transport capability. Moreover, this facile Nb 4+ -assisted synthetic route has demonstrated to be general, which can be applied to load other metals such as Au and Pt on monolayer HNb 3 O 8 NS. It is anticipated that this work can extend the facile preparation of noble metal/nanosheet 2D heterostructures, as well as promote the simultaneous capture of duple renewable thermal and photon energy sources to drive an energy efficient

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.

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%.

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.

Metal resistance or tolerance? Acidophiles confront high metal loads via both abiotic and biotic mechanisms

Directory of Open Access Journals (Sweden)

Mark eDopson

2014-04-01

Full Text Available All metals are toxic at high concentrations and consequently their intracellular concentrations must be regulated. Acidophilic microorganisms have an optimum growth pH < 3 and proliferate in natural and anthropogenic low pH environments. Some acidophiles are involved in the catalysis of sulfide mineral dissolution, resulting in high concentrations of metals in solution. Acidophiles are often described as highly metal resistant via mechanisms such as multiple and/or more efficient active resistance systems than are present in neutrophiles. However, this is not the case for all acidophiles and we contend that their growth in high metal concentrations is partially due to an intrinsic tolerance as a consequence of the environment in which they live. In this perspective, we highlight metal tolerance via complexation of free metals by sulfate ions and passive tolerance to metal influx via an internal positive cytoplasmic transmembrane potential. These tolerance mechanisms have been largely ignored in past studies of acidophile growth in the presence of metals and should be taken into account.

Atomic bonding between metal and graphene

KAUST Repository

Wang, Hongtao

2013-03-07

To understand structural and chemical properties of metal-graphene composites, it is crucial to unveil the chemical bonding along the interface. We provide direct experimental evidence of atomic bonding between typical metal nano structures and graphene, agreeing well with density functional theory studies. Single Cr atoms are located in the valleys of a zigzag edge, and few-atom ensembles preferentially form atomic chains by self-assembly. Low migration barriers lead to rich dynamics of metal atoms and clusters under electron irradiation. We demonstrate no electron-instigated interaction between Cr clusters and pristine graphene, though Cr has been reported to be highly reactive to graphene. The metal-mediated etching is a dynamic effect between metal clusters and pre-existing defects. The resolved atomic configurations of typical nano metal structures on graphene offer insight into modeling and simulations on properties of metal-decorated graphene for both catalysis and future carbon-based electronics. © 2013 American Chemical Society.

Characterizing heterogeneous dynamics at hydrated electrode surfaces

Science.gov (United States)

Willard, Adam P.; Limmer, David T.; Madden, Paul A.; Chandler, David

2013-05-01

In models of Pt 111 and Pt 100 surfaces in water, motions of molecules in the first hydration layer are spatially and temporally correlated. To interpret these collective motions, we apply quantitative measures of dynamic heterogeneity that are standard tools for considering glassy systems. Specifically, we carry out an analysis in terms of mobility fields and distributions of persistence times and exchange times. In so doing, we show that dynamics in these systems is facilitated by transient disorder in frustrated two-dimensional hydrogen bonding networks. The frustration is the result of unfavorable geometry imposed by strong metal-water bonding. The geometry depends upon the structure of the underlying metal surface. Dynamic heterogeneity of water on the Pt 111 surface is therefore qualitatively different than that for water on the Pt 100 surface. In both cases, statistics of this ad-layer dynamic heterogeneity responds asymmetrically to applied voltage.

Characterizing heterogeneous dynamics at hydrated electrode surfaces.

Science.gov (United States)

Willard, Adam P; Limmer, David T; Madden, Paul A; Chandler, David

2013-05-14

In models of Pt 111 and Pt 100 surfaces in water, motions of molecules in the first hydration layer are spatially and temporally correlated. To interpret these collective motions, we apply quantitative measures of dynamic heterogeneity that are standard tools for considering glassy systems. Specifically, we carry out an analysis in terms of mobility fields and distributions of persistence times and exchange times. In so doing, we show that dynamics in these systems is facilitated by transient disorder in frustrated two-dimensional hydrogen bonding networks. The frustration is the result of unfavorable geometry imposed by strong metal-water bonding. The geometry depends upon the structure of the underlying metal surface. Dynamic heterogeneity of water on the Pt 111 surface is therefore qualitatively different than that for water on the Pt 100 surface. In both cases, statistics of this ad-layer dynamic heterogeneity responds asymmetrically to applied voltage.

Gasification of carbon deposits on catalysts and metal surfaces

Energy Technology Data Exchange (ETDEWEB)

Figueiredo, J L

1986-10-01

'Coke' deposited on catalysts and reactor surfaces includes a variety of carbons of different structures and origins, their reactivities being conveniently assessed by Temperature Programmed Reaction (TPR). The gasification of carbon deposits obtained in the laboratory under well controlled conditions, and the regeneration of coked catalysts from petroleum refining processes are reviewed and discussed. Filamentary carbon deposits, containing dispersed metal particles, behave as supported metal catalysts during gasification, and show high reactivities. Pyrolytic and acid catalysis carbons are less reactive on their own, as the gasification is not catalysed; however, metal components of the catalyst or metal impurities deposited on the surface may enhance gasification. 26 refs., 8 figs., 2 tabs.

Solid Acid Catalysts for Coumarin Synthesis by the Pechmann Reaction: MOFs versus Zeolites

Czech Academy of Sciences Publication Activity Database

Opanasenko, Maksym; Shamzhy, Mariya; Čejka, Jiří

2013-01-01

Roč. 5, č. 4 (2013), s. 1024-1031 ISSN 1867-3880 R&D Projects: GA ČR GBP106/12/G015 Grant - others:European Commission(XE) FP7/2007-2013, contract 228862 Institutional support: RVO:61388955 Keywords : mesoporous molecular sieves * metal -organic frameworks * heterogeneous catalysis Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.044, year: 2013

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...

Stereodirection of an α-ketoester at sub-molecular sites on chirally modified Pt(111): Heterogeneous asymmetric catalysis

DEFF Research Database (Denmark)

Demers-Carpentier, V.; Rasmussen, A.M.H.; Goubert, G.

2013-01-01

Chirally modified Pt catalysts are used in the heterogeneous asymmetric hydrogenation of α-ketoesters. Stereoinduction is believed to occur through the formation of chemisorbed modifier–substrate complexes. In this study, the formation of diastereomeric complexes by coadsorbed methyl 3,3,3-triflu......Chirally modified Pt catalysts are used in the heterogeneous asymmetric hydrogenation of α-ketoesters. Stereoinduction is believed to occur through the formation of chemisorbed modifier–substrate complexes. In this study, the formation of diastereomeric complexes by coadsorbed methyl 3...

Metal-hydrogen systems with an exceptionally large and tunable thermodynamic destabilization

NARCIS (Netherlands)

Ngene, Peter; Longo, Alessandro; Mooij, L.P.A.; Bras, Wim; Dam, B.

2017-01-01

Hydrogen is a key element in the energy transition. Hydrogen-metal systems have been studied for various energy-related applications, e.g., for their use in reversible hydrogen storage, catalysis, hydrogen sensing, and rechargeable batteries. These applications depend strongly on the

The uncertainties calculation of acoustic method for measurement of dissipative properties of heterogeneous non-metallic materials

Directory of Open Access Journals (Sweden)

Мaryna O. Golofeyeva

2015-12-01

Full Text Available The effective use of heterogeneous non-metallic materials and structures needs measurement of reliable values of dissipation characteristics, as well as common factors of their change during the loading process. Aim: The aim of this study is to prepare the budget for measurement uncertainty of dissipative properties of composite materials. Materials and Methods: The method used to study the vibrational energy dissipation characteristics based on coupling of vibrations damping decrement and acoustic velocity in a non-metallic heterogeneous material is reviewed. The proposed method allows finding the dependence of damping on vibrations amplitude and frequency of strain-stress state of material. Results: Research of the accuracy of measurement method during the definition of decrement attenuation of fluctuations in synthegran was performed. The international approach for evaluation of measurements quality is used. It includes the common practice international rules for uncertainty expression and their summation. These rules are used as internationally acknowledged confidence measure to the measurement results, which includes testing. The uncertainties budgeting of acoustic method for measurement of dissipative properties of materials were compiled. Conclusions: It was defined that there are two groups of reasons resulting in errors during measurement of materials dissipative properties. The first group of errors contains of parameters changing of calibrated bump in tolerance limits, displacement of sensor in repeated placement to measurement point, layer thickness variation of contact agent because of irregular hold-down of resolvers to control surface, inaccuracy in reading and etc. The second group of errors is linked with density and Poisson’s ratio measurement errors, distance between sensors, time difference between signals of vibroacoustic sensors.

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.

Platinum clusters with precise numbers of atoms for preparative-scale catalysis.

Science.gov (United States)

Imaoka, Takane; Akanuma, Yuki; Haruta, Naoki; Tsuchiya, Shogo; Ishihara, Kentaro; Okayasu, Takeshi; Chun, Wang-Jae; Takahashi, Masaki; Yamamoto, Kimihisa

2017-09-25

Subnanometer noble metal clusters have enormous potential, mainly for catalytic applications. Because a difference of only one atom may cause significant changes in their reactivity, a preparation method with atomic-level precision is essential. Although such a precision with enough scalability has been achieved by gas-phase synthesis, large-scale preparation is still at the frontier, hampering practical applications. We now show the atom-precise and fully scalable synthesis of platinum clusters on a milligram scale from tiara-like platinum complexes with various ring numbers (n = 5-13). Low-temperature calcination of the complexes on a carbon support under hydrogen stream affords monodispersed platinum clusters, whose atomicity is equivalent to that of the precursor complex. One of the clusters (Pt 10 ) exhibits high catalytic activity in the hydrogenation of styrene compared to that of the other clusters. This method opens an avenue for the application of these clusters to preparative-scale catalysis.The catalytic activity of a noble metal nanocluster is tied to its atomicity. Here, the authors report an atom-precise, fully scalable synthesis of platinum clusters from molecular ring precursors, and show that a variation of only one atom can dramatically change a cluster's reactivity.

Liquid metals: fundamentals and applications in chemistry.

Science.gov (United States)

Daeneke, T; Khoshmanesh, K; Mahmood, N; de Castro, I A; Esrafilzadeh, D; Barrow, S J; Dickey, M D; Kalantar-Zadeh, K

2018-04-03

Post-transition elements, together with zinc-group metals and their alloys belong to an emerging class of materials with fascinating characteristics originating from their simultaneous metallic and liquid natures. These metals and alloys are characterised by having low melting points (i.e. between room temperature and 300 °C), making their liquid state accessible to practical applications in various fields of physical chemistry and synthesis. These materials can offer extraordinary capabilities in the synthesis of new materials, catalysis and can also enable novel applications including microfluidics, flexible electronics and drug delivery. However, surprisingly liquid metals have been somewhat neglected by the wider research community. In this review, we provide a comprehensive overview of the fundamentals underlying liquid metal research, including liquid metal synthesis, surface functionalisation and liquid metal enabled chemistry. Furthermore, we discuss phenomena that warrant further investigations in relevant fields and outline how liquid metals can contribute to exciting future applications.

Mo-II Cluster Complex-Based Coordination Polymer as an Efficient Heterogeneous Catalyst in the Suzuki–Miyaura Coupling Reaction

Czech Academy of Sciences Publication Activity Database

Bůžek, Daniel; Hynek, Jan; Kučeráková, Monika; Kirakci, Kaplan; Demel, Jan; Lang, Kamil

2016-01-01

Roč. 2016, č. 28 (2016), s. 4668-4673 ISSN 1434-1948 R&D Projects: GA ČR GA13-05114S; GA ČR GA15-12653S EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:61388980 ; RVO:68378271 Keywords : C–C coupling * Heterogeneous catalysis * Molybdenum * Palladium * Polymers Subject RIV: CA - Inorganic Chemistry ; CF - Physical ; Theoretical Chemistry (FZU-D) Impact factor: 2.444, year: 2016

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...

Light-enhanced acid catalysis over a metal-organic framework.

Science.gov (United States)

Xu, Caiyun; Sun, Keju; Zhou, Yu-Xiao; Ma, Xiao; Jiang, Hai-Long

2018-03-06

A Brønsted acid-functionalized metal-organic framework (MOF), MIL-101-SO 3 H, was prepared for acid-engaged esterification reactions. Strikingly, for the first time, the MOF exhibits significantly light-enhanced activity and possesses excellent activity and recyclability, with even higher activity than H 2 SO 4 under light irradiation.

The limited role of aquifer heterogeneity on metal reduction in an Atlantic coastal plain determined by push-pull tests

International Nuclear Information System (INIS)

Mailloux, Brian J.; Devlin, Stephanie; Fuller, Mark E.; Onstott, T.C.; De Flaun, Mary F.; Choi, K.-H.; Green-Blum, Maria; Swift, Donald J.P.; McCarthy, John; Dong Hailiang

2007-01-01

Sixty push-pull experiments were conducted to determine the factors controlling Fe(III) and Mn(IV) reduction in a well-characterized, shallow, coastal plain aquifer near Oyster, VA, USA. The five multi-level samplers each equipped with 12 ports sampled a heterogeneous portion of the aquifer from 4.4 to 8m-bgs. Each multi-level sampler (MLS) was injected with groundwater that contained NO 3 - and Br - along with: (1) just groundwater (control treatment), (2) humics, (3) lactate (conducted twice) and (4) lactate plus humics. Microbially mediated Fe(III) reduction caused the aqueous Fe Tot concentrations to increase at every depth in the lactate treatment with significant increases within 1 day even while NO 3 - was present. Little change in the Fe Tot concentrations were observed in the control and humics treatment. Humics may have acted as an electron shuttle to increase Fe(III) reduction in the lactate plus humics treatment. The amount of Mn(IV) reduction was significantly lower than that of Fe(III) reduction. Geochemical modeling indicated that gas formation, sorption on reactive surfaces, and mineral precipitation were important processes and that Fe(III) and SO 4 2- reduction were co-occurring. Conditions were favorable for the precipitation of Fe-carbonates, Fe-sulfides and Fe-silicates. In the lactate treatment protist concentrations increased then decreased and planktonic cell concentrations steadily increased, whereas no change was observed in the control treatment. Correlations of Fe(III) reduction with physical and chemical heterogeneity were weak, probably as a result of the abundance of Fe(III) bearing minerals relative to electron donor abundance and that the push-pull test sampled a representative elemental volume that encompassed the microbial diversity within the aquifer. This work indicates that stimulating metal reduction in aquifer systems is a feasible method for remediating heterogeneous subsurface sites contaminated with metals and

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...

Universality in heterogeneous catalysis

DEFF Research Database (Denmark)

Nørskov, Jens Kehlet; Pedersen, Thomas Bligaard; Logadottir, Ashildur

2002-01-01

Based on an extensive set of density functional theory calculations it is shown that for a class of catalytic reactions there is a universal, reactant independent relation between the reaction activation energy and the stability of reaction intermediates. This leads directly to a universal relati...

Preparation of a Composite of Sulfated Zirconia/Metal Organic Framework and its Application in Esterification Reaction

Energy Technology Data Exchange (ETDEWEB)

Park, Eun Young; Hasan, Zubair; Ahmed, Imteaz; Jhung, Sung Hwa [Kyungpook National Univ., Daegu (Korea, Republic of)

2014-06-15

A porous metal-organic framework (MOF), MIL-101, was synthesized in the presence of sulfated zirconia (SZ) to produce acidic SZ/MIL-101 composites for the first time. The composites were characterized with XRD, nitrogen adsorption, FT-IR, scanning electron microscope, chemical analysis and so on. The composites (SZ/MIL-101s) were successfully applied in a liquid-phase esterification for a high yield of ester. This catalytic result of SZ/MIL-101, compared with that of pure SZ or MIL-101 (showing a negligible yield of ester), suggests that the SZ in the composite is highly active in the acid catalysis probably because of the well-dispersed active species of SZ. Moreover, the esterification is catalyzed in heterogeneous mode as confirmed by negligible esterification after filtration of the catalyst. Finally, microwaves can be efficiently applied both in the synthesis of the composites and the esterification reaction to accelerate the two processes of synthesis and esterification by about 5 times.

Preparation of a Composite of Sulfated Zirconia/Metal Organic Framework and its Application in Esterification Reaction

International Nuclear Information System (INIS)

Park, Eun Young; Hasan, Zubair; Ahmed, Imteaz; Jhung, Sung Hwa

2014-01-01

A porous metal-organic framework (MOF), MIL-101, was synthesized in the presence of sulfated zirconia (SZ) to produce acidic SZ/MIL-101 composites for the first time. The composites were characterized with XRD, nitrogen adsorption, FT-IR, scanning electron microscope, chemical analysis and so on. The composites (SZ/MIL-101s) were successfully applied in a liquid-phase esterification for a high yield of ester. This catalytic result of SZ/MIL-101, compared with that of pure SZ or MIL-101 (showing a negligible yield of ester), suggests that the SZ in the composite is highly active in the acid catalysis probably because of the well-dispersed active species of SZ. Moreover, the esterification is catalyzed in heterogeneous mode as confirmed by negligible esterification after filtration of the catalyst. Finally, microwaves can be efficiently applied both in the synthesis of the composites and the esterification reaction to accelerate the two processes of synthesis and esterification by about 5 times

Design considerations for large heterogeneous liquid-metal fast breeder reactors

International Nuclear Information System (INIS)

Tzanos, C.P.; Barthold, W.P.

1977-01-01

A systematic method for designing heterogeneous configurations having a near-zero value of sodium void reactivity is presented. It is based on the following principles: (a) the thickness of the internal blanket zones should be such that the reactivity change resulting from voiding any core zone is practically independent of any further increase in the thickness of these zones, and (b) the sodium void reactivity of each core zone must have a near-zero value. Neutronic coupling among the core zones of heterogeneous configurations decreases as the thickness of the internal blanket zones increases. To quantify coupling, Avery's coupling coefficients are used. Reduced coupling among the core zones of a heterogeneous design, compared to a homogeneous design, results in (a) increased sensitivity of the power distribution to enrichment distribution perturbations, (b) reduced reactivity worth of local perturbations, and (c) higher cladding temperatures during operational transients initiated by local perturbations. Heterogeneous designs compared to equivalent homogeneous designs have (a) lower core Doppler coefficient values, (b) larger fuel compaction reactivities, and (c) higher maximum cladding temperatures

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...

Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts

International Nuclear Information System (INIS)

Wang, Hongliang; Wang, Huamin; Kuhn, Eric; Tucker, Melvin P.; Yang, Bin

2017-01-01

Super Lewis acids containing the triflate anion [e.g., Hf(OTf) 4 , Ln(OTf) 3 , In(OTf) 3 , Al(OTf) 3 ] and noble metal catalysts (e.g., Ru/C, Ru/Al2O 3 ) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage through selective bonding to etheric oxygens while the noble metal catalyzed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf)4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt % of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates by protonating hydroxyl groups and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote oxygenation reactions catalyzed by super Lewis acids.

Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts

Energy Technology Data Exchange (ETDEWEB)

Wang, Hongliang [Department of Biological Systems Engineering, Washington State University, Richland WA 99354 USA; Current address: Center of Biomass Engineering/College of Agronomy and Biotechnology, China Agricultural University, Beijing 100193 PR China; Wang, Huamin [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99354 USA; Kuhn, Eric [National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway Golden CO 80401 USA; Tucker, Melvin P. [National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway Golden CO 80401 USA; Yang, Bin [Department of Biological Systems Engineering, Washington State University, Richland WA 99354 USA

2017-11-14

Super Lewis acids containing the triflate anion (e.g. Hf(OTf)4, Ln(OTf)3, Al(OTf)3) and noble metal catalysts (e.g. Ru/C, Ru/Al2O3) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage via selective bonding to etheric oxygens while the noble metal catalysed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf)4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt% of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates via protonating hydroxyls and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote oxygenation reactions catalysed by super Lewis acids.

Metal complex catalysis in the synthesis of organoaluminium compounds

International Nuclear Information System (INIS)

Dzhemilev, Usein M; Ibragimov, Askhat G

2000-01-01

The published data on the synthesis of organoaluminium compounds involving metal complex catalysts are generalised and systematised. Hydro-, carbo- and cycloalumination reactions of alkenes, conjugated dienes and alkynes catalysed by Ti and Zr complexes are considered in detail. The use of organoaluminium reagents in organic synthesis and novel reactions involving these compounds are discussed. The bibliography includes 240 references.

Copper plasmonics and catalysis: role of electron-phonon interactions in dephasing localized surface plasmons

Science.gov (United States)

Sun, Qi-C.; Ding, Yuchen; Goodman, Samuel M.; H. Funke, Hans; Nagpal, Prashant

2014-10-01

Copper metal can provide an important alternative for the development of efficient, low-cost and low-loss plasmonic nanoparticles, and selective nanocatalysts. However, poor chemical stability and lack of insight into photophysics and plasmon decay mechanisms has impeded study. Here, we use smooth conformal ALD coating on copper nanoparticles to prevent surface oxidation, and study dephasing time for localized surface plasmons on different sized copper nanoparticles. Using dephasing time as a figure of merit, we elucidate the role of electron-electron, electron-phonon, impurity, surface and grain boundary scattering on the decay of localized surface plasmon waves. Using our quantitative analysis and different temperature dependent measurements, we show that electron-phonon interactions dominate over other scattering mechanisms in dephasing plasmon waves. While interband transitions in copper metal contributes substantially to plasmon losses, tuning surface plasmon modes to infrared frequencies leads to a five-fold enhancement in the quality factor. These findings demonstrate that conformal ALD coatings can improve the chemical stability for copper nanoparticles, even at high temperatures (>300 °C) in ambient atmosphere, and nanoscaled copper is a good alternative material for many potential applications in nanophotonics, plasmonics, catalysis and nanoscale electronics.Copper metal can provide an important alternative for the development of efficient, low-cost and low-loss plasmonic nanoparticles, and selective nanocatalysts. However, poor chemical stability and lack of insight into photophysics and plasmon decay mechanisms has impeded study. Here, we use smooth conformal ALD coating on copper nanoparticles to prevent surface oxidation, and study dephasing time for localized surface plasmons on different sized copper nanoparticles. Using dephasing time as a figure of merit, we elucidate the role of electron-electron, electron-phonon, impurity, surface and grain

A general chelate-assisted co-assembly to metallic nanoparticles-incorporated ordered mesoporous carbon catalysts for Fischer-Tropsch synthesis.

Science.gov (United States)

Sun, Zhenkun; Sun, Bo; Qiao, Minghua; Wei, Jing; Yue, Qin; Wang, Chun; Deng, Yonghui; Kaliaguine, Serge; Zhao, Dongyuan

2012-10-24

The organization of different nano objects with tunable sizes, morphologies, and functions into integrated nanostructures is critical to the development of novel nanosystems that display high performances in sensing, catalysis, and so on. Herein, using acetylacetone as a chelating agent, phenolic resol as a carbon source, metal nitrates as metal sources, and amphiphilic copolymers as a template, we demonstrate a chelate-assisted multicomponent coassembly method to synthesize ordered mesoporous carbon with uniform metal-containing nanoparticles. The obtained nanocomposites have a 2-D hexagonally arranged pore structure, uniform pore size (~4.0 nm), high surface area (~500 m(2)/g), moderate pore volume (~0.30 cm(3)/g), uniform and highly dispersed Fe(2)O(3) nanoparticles, and constant Fe(2)O(3) contents around 10 wt %. By adjusting acetylacetone amount, the size of Fe(2)O(3) nanoparticles is readily tunable from 8.3 to 22.1 nm. More importantly, it is found that the metal-containing nanoparticles are partially embedded in the carbon framework with the remaining part exposed in the mesopore channels. This unique semiexposure structure not only provides an excellent confinement effect and exposed surface for catalysis but also helps to tightly trap the nanoparticles and prevent aggregating during catalysis. Fischer-Tropsch synthesis results show that as the size of iron nanoparticles decreases, the mesoporous Fe-carbon nanocomposites exhibit significantly improved catalytic performances with C(5+) selectivity up to 68%, much better than any reported promoter-free Fe-based catalysts due to the unique semiexposure morphology of metal-containing nanoparticles confined in the mesoporous carbon matrix.

Theory meets experiment: Gas-phase chemistry of coinage metals

Czech Academy of Sciences Publication Activity Database

Roithová, J.; Schröder, Detlef

2009-01-01

Roč. 253, 5/6 (2009), s. 666-677 ISSN 0010-8545 R&D Projects: GA AV ČR KJB400550704; GA ČR GA203/08/1487 Institutional research plan: CEZ:AV0Z40550506 Keywords : catalysis * coinage metals * copper * gold * mass spectrometry Subject RIV: CC - Organic Chemistry Impact factor: 11.225, year: 2009

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.

Heterogeneous composite bodies with isolated lenticular shaped cermet regions

Science.gov (United States)

Sherman, Andrew J [Cirtland Hills, OH

2009-12-22

A heterogeneous body having ceramic rich cermet regions in a more ductile metal matrix. The heterogeneous bodies are formed by thermal spray operations on metal substrates. The thermal spray operations apply heat to a cermet powder and project it onto a solid substrate. The cermet powder is composed of complex composite particles in which a complex ceramic-metallic core particle is coated with a matrix precursor. The cermet regions are generally comprised of complex ceramic-metallic composites that correspond approximately to the core particles. The cermet regions are approximately lenticular shaped with an average width that is at least approximately twice the average thickness. The cermet regions are imbedded within the matrix phase and generally isolated from one another. They have obverse and reverse surfaces. The matrix phase is formed from the matrix precursor coating on the core particles. The amount of heat applied during the formation of the heterogeneous body is controlled so that the core particles soften but do not become so fluid that they disperse throughout the matrix phase. The force of the impact on the surface of the substrate tends to flatten them. The flattened cermet regions tend to be approximately aligned with one another in the body.

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

A polyoxometalate-encapsulating cationic metal-organic framework as a heterogeneous catalyst for desulfurization.

Science.gov (United States)

Hao, Xiu-Li; Ma, Yuan-Yuan; Zang, Hong-Ying; Wang, Yong-Hui; Li, Yang-Guang; Wang, En-Bo

2015-02-23

A new cationic triazole-based metal-organic framework encapsulating Keggin-type polyoxometalates, with the molecular formula [Co(BBPTZ)3][HPMo12O40]⋅24 H2O [compound 1; BBPTZ = 4,4'-bis(1,2,4-triazol-1-ylmethyl)biphenyl] is hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, powder X-ray diffraction, and single-crystal X-ray diffraction. The structure of compound 1 contains a non-interpenetrated 3D CdSO4 (cds)-type framework with two types of channels that are interconnected with each other; straight channels that are occupied by the Keggin-type POM anions, and wavelike channels that contain lattice water molecules. The catalytic activity of compound 1 in the oxidative desulfurization reaction indicates that it is not only an effective and size-selective heterogeneous catalyst, but it also exhibits distinct structural stability in the catalytic reaction system. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis, characterizations and catalytic studies of a new two-dimensional metal-organic framework based on Co-carboxylate secondary building units

Science.gov (United States)

Bagherzadeh, Mojtaba; Ashouri, Fatemeh; Đaković, Marijana

2015-03-01

A metal-organic framework [Co3(BDC)3(DMF)2(H2O)2] was synthesized and structurally characterized. X-ray single crystal analysis revealed that the framework contains a 2D polymeric chain through coordination of 1,4-benzenedicarboxylic acid linker ligand to cobalt centers. The polymer crystallize in monoclinic P21/n space group with a=13.989(3) Å, b=9.6728(17) Å, c=16.707(3) Å, and Z=2. The polymer features a framework based on the perfect octahedral Co-O6 secondary building units. The catalytic activities of [Co3(BDC)3(DMF)2(H2O)2]n for olefins oxidation was conducted. The heterogeneous catalyst could be facilely separated from the reaction mixture, and reused three times without significant degradation in catalytic activity. Furthermore, no contribution from homogeneous catalysis of active species leaching into reaction solution was detected.

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...

Generation, Detection and characterization of Gas-Phase Transition Metal containing Molecules

Energy Technology Data Exchange (ETDEWEB)

Steimle, Timothy [Arizona State Univ., Tempe, AZ (United States)

2015-12-15

The objective of this project was to generate, detect, and characterize small, gas-phase, metal containing molecules. In addition to being relevant to high temperature chemical environments (e.g. plasmas and combustion), gas-phase experiments on metal containing molecules serve as the most direct link to a molecular-level theoretical model for catalysis. Catalysis (i.e. the addition of a small about of recoverable material to control the rate and direction of a chemical reaction) is critical to the petroleum and pharmaceutical industries as well as environmental remediation. Currently, the majority of catalytic materials are based on very expensive metals such as platinum (Pt), palladium (Pd), iridium (Ir,) rhenium (Re), and rhodium (Rh). For example, the catalyst used for converting linear hydrocarbon molecules (e.g. hexane) to cyclic molecules (e.g. cyclohexane) is a mixture of Pt and Re suspended on alumina. It enables straight chain alkanes to be converted into branched-chain alkanes, cyclohexanes and aromatic hydrocarbons which are used, amongst other things, to enhance the octane number of petrol. A second example is the heterogeneous catalysis used in automobile exhaust systems to: a) decrease nitrogen oxide; b) reduce carbon monoxide; and c) oxidize unburned hydrocarbons. The exhaust is vented through a high-surface area chamber lined with Pt, Pd, and Rh. For example, the carbon monoxide is catalytically converted to carbon dioxide by reaction with oxygen. The research results from this work have been published in readily accessible journals1-28. The ground and excited electronic state properties of small metal containing molecules that we determine were: a) electronic state distributions and lifetimes, b) vibrational frequencies, c) bond lengths and angles, d) hyperfine interactions, e) permanent electric dipole moments, mel, and f) magnetic dipoles, μ_m. In general terms, μ_el, gives insight into the charge distribution and mm into

Micro-reactor for heterogeneous catalysis. Application: hydrogen production from methyl-cyclohexane; Microreacteur pour la catalyse heterogene. Application: production d'hydrogene a partir du methylcyclohexane

Energy Technology Data Exchange (ETDEWEB)

Roumanie, M.; Pijolat, C. [Ecole des Mines de Saint Etienne, Centre SPIN (DMICC/LPMG/URA/CNRS-D2021), 42 - Saint Etienne (France); Meille, V.; Bellefon, C. de [Centre National de la Recherche Scientifique (CNRS/CPE), Lab. de Genie des Procedes Catalytiques, 69 - Villeurbanne (France); Pouteau, P.; Delattre, C. [CEA Grenoble, Lab. d' Electronique et de Technologie de l' Informatique (LETI), 38 (France)

2004-07-01

First developed by the pharmaceutical industry to find new drugs (combinatorial analysis), the lab on chip is also extremely interesting for the catalysis field. This major interest comes from the miniaturize size and the high surface on volume ratio which lead to improve mass and heat transfer but also the safety in regards of industrial application. The use of micro-technology and the miniaturization of various systems such as micro-fuel cell is also a current field of activity. So for the future research the production of hydrogen is a point to develop in order to supply a micro-fuel cell. The aim of this work is to study and to realize an autonomous catalytic micro-reactor for hydrogen production from methyl-cyclohexane. For this reaction of dehydrogenation, the common catalyst is platinum supported on alumina. Consequently, the general objectives of this work are: 1)to develop a micro-reactor with its heaters, sensors...2)to deposit catalysts in the micro-reactor 3)to study the catalytic conversion of this system.

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

Science.gov (United States)

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

2018-06-13

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

The ultrasound-assisted oxidative scission of monoenic fatty acids by ruthenium tetroxide catalysis: influence of the mixture of solvents.

Science.gov (United States)

Rup, Sandrine; Zimmermann, François; Meux, Eric; Schneider, Michel; Sindt, Michele; Oget, Nicolas

2009-02-01

Carboxylic acids and diacids were synthesized from monoenic fatty acids by using RuO4 catalysis, under ultrasonic irradiation, in various mixtures of solvents. Ultrasound associated with Aliquat 336 have promoted in water, the quantitative oxidative cleavage of the CH=CH bond of oleic acid. A design of experiment (DOE) shows that the optimal mixture of solvents (H2O/MeCN, ratio 1/1, 2.2% RuCl3/4.1 eq. NaIO4) gives 81% azelaic acid and 97% pelargonic acid. With the binary heterogeneous mixture H2O/AcOEt, the oxidation of the oleic acid leads to a third product, the alpha-dione 9,10-dioxostearic acid.

Heterogeneous photo-Fenton oxidation with natural clays for phenol and tyrosol remediation

Directory of Open Access Journals (Sweden)

Djeffal L.

2013-09-01

Full Text Available Due to their excellent properties, clays have been widely used in several applications, particularly in catalysis. In this paper, three clays were used as heterogeneous photo-Fenton catalysts for phenol and tyrosol oxidations. Particular attention was given to the effect of the main operating conditions on the process performance. A total conversion was obtained for both organic pollutants with studied catalysts in 20 minutes reaction. For phenol, a total organic carbon (TOC conversion of 93% was obtained using sieved and calcined smectite clay. The TOC conversion was 60% for tyrosol with the same catalyst. Clays were characterized by chemical analysis, BET, XRD, TPR and SEM.

Applications of Immobilized Bio-Catalyst in Metal-Organic Frameworks

Directory of Open Access Journals (Sweden)

Qi Wang

2018-04-01

Full Text Available Immobilization of bio-catalysts in solid porous materials has attracted much attention in the last few decades due to its vast application potential in ex vivo catalysis. Despite the high efficiency and selectivity of enzymatic catalytic processes, enzymes may suffer from denaturation under industrial production conditions, which, in turn, diminish their catalytic performances and long-term recyclability. Metal-organic frameworks (MOFs, as a growing type of hybrid materials, have been identified as promising platforms for enzyme immobilization owing to their enormous structural and functional tunability, and extraordinary porosity. This review mainly focuses on the applications of enzyme@MOFs hybrid materials in catalysis, sensing, and detection. The improvements of catalytic activity and robustness of encapsulated enzymes over the free counterpart are discussed in detail.

Catalysis by Design Using Surface Organometallic Nitrogen-Containing Fragments

KAUST Repository

Hamzaoui, Bilel

2016-06-14

The aim of this thesis is to explore the chemistry of well-defined silica-supported group 4 and group 5 complexes that contain one or more multiply-bonded nitrogen atoms. Such species have been recognized as crucial intermediates in many catalytic reactions (e.g. hydroaminoalkylation, olefin hydrogenation, imine metathesis…). The first chapter provided a bibliographic overview of the preparation and the reactivity of group 4 and 5 complexes towards hydroaminoalkylation and imine metathesis catalysis. The second chapter deals with the isolation and the characterization of a series of well-defined group 4 ƞ2-imine complexes surfaces species. 2D solid-state NMR (1H–13C HETCOR, Multiple Quantum) experiments have revealed consistently a unique structural rearrangement, viz azametallacycle occurring on the immobilized metal-amido ligands. Hydrogenolysis of the sole Zr-C bond in such species gives selectively a silica-supported zirconium monohydride that can perform the catalytic hydrogenation of olefins. The third chapter examines the mechanistic studies of the intermolecular hydroaminoalkylation using SOMC to identify the key metallacyclic surface intermediates (silica-supported three-membred and five-membered). The catalyst was regenerated by protonolysis and afforded pure amine. Catalytic testing of a selection of amine compounds with variable electronic properties was carried out. The fourth chapter deals with the generation and the characterization of well-defined silica-supported zirconium-imido complexes. The resulting species effectively catalyzes imine/imine cross-metathesis and thus considered as the first heterogeneous catalysts active for imine metathesis reaction. The fifth chapter studies the reaction of SBA15.1100 ºC with dry aniline and derivatives leading to opening strained siloxane bridges into acid-base paired functionalities (formation of N-phenylsilanamine-silanol pairs). This approach was successfully applied to the design of a series of

Nanoscale heterostructures with molecular-scale single-crystal metal wires.

Science.gov (United States)

Kundu, Paromita; Halder, Aditi; Viswanath, B; Kundu, Dipan; Ramanath, Ganpati; Ravishankar, N

2010-01-13

Creating nanoscale heterostructures with molecular-scale (synthesis of nanoscale heterostructures with single-crystal molecular-scale Au nanowires attached to different nanostructure substrates. Our method involves the formation of Au nanoparticle seeds by the reduction of rocksalt AuCl nanocubes heterogeneously nucleated on the substrates and subsequent nanowire growth by oriented attachment of Au nanoparticles from the solution phase. Nanoscale heterostructures fabricated by such site-specific nucleation and growth are attractive for many applications including nanoelectronic device wiring, catalysis, and sensing.

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)

Metal Oxide/Graphene Composites for Supercapacitive Electrode Materials.

Science.gov (United States)

Jeong, Gyoung Hwa; Baek, Seungmin; Lee, Seungyeol; Kim, Sang-Wook

2016-04-05

Graphene composites with metal or metal oxide nanoparticles have been extensively investigated owing to their potential applications in the fields of fuel cells, batteries, sensing, solar cells, and catalysis. Among them, much research has focused on supercapacitor applications and have come close to realization. Composites include monometal oxides of cobalt, nickel, manganese, and iron, as well as their binary and ternary oxides. In addition, their morphological control and hybrid systems of carbon nanotubes have also been investigated. This review presents the current trends in research on metal oxide/graphene composites for supercapacitors. Furthermore, methods are suggested to improve the properties of electrochemical capacitor electrodes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Recent Advances in Transition-Metal-Mediated Electrocatalytic CO2 Reduction: From Homogeneous to Heterogeneous Systems

Directory of Open Access Journals (Sweden)

Da-Ming Feng

2017-12-01

Full Text Available Global climate change and increasing demands for clean energy have brought intensive interest in the search for proper electrocatalysts in order to reduce carbon dioxide (CO2 to higher value carbon products such as hydrocarbons. Recently, transition-metal-centered molecules or organic frameworks have been reported to show outstanding electrocatalytic activity in the liquid phase. Their d-orbital electrons are believed to be one of the key factors to capture and convert CO2 molecules to value-added low-carbon fuels. In this review, recent advances in electrocatalytic CO2 reduction have been summarized based on the targeted products, ranging from homogeneous reactions to heterogeneous ones. Their advantages and fallbacks have been pointed out and the existing challenges, especially with respect to the practical and industrial application are addressed.

Recent Advances in Transition-Metal-Mediated Electrocatalytic CO2 Reduction: From Homogeneous to Heterogeneous Systems

KAUST Repository

Feng, Da-Ming

2017-12-01

Global climate change and increasing demands for clean energy have brought intensive interest in the search for proper electrocatalysts in order to reduce carbon dioxide (CO2) to higher value carbon products such as hydrocarbons. Recently, transition-metal-centered molecules or organic frameworks have been reported to show outstanding electrocatalytic activity in the liquid phase. Their d-orbital electrons are believed to be one of the key factors to capture and convert CO2 molecules to value-added low-carbon fuels. In this review, recent advances in electrocatalytic CO2 reduction have been summarized based on the targeted products, ranging from homogeneous reactions to heterogeneous ones. Their advantages and fallbacks have been pointed out and the existing challenges, especially with respect to the practical and industrial application are addressed.

Template-directed synthesis of oligoguanylic acids - Metal ion catalysis

Science.gov (United States)

Bridson, P. K.; Fakhrai, H.; Lohrmann, R.; Orgel, L. E.; Van Roode, M.

1981-01-01

The effects of Zn(2+), Pb(2+) and other metal ions on the efficiency and stereo-selectivity of the template-directed oligomerization of guanosine 5'-phosphorimidazolide are investigated. Reactions were run in the presence of a polyC template in a 2,6-lutidine buffer, and products analyzed by high-performance liquid chromatography on an RPC-5 column. The presence of the Pb(2+) ion is found to lead to the formation of 2'-5' linked oligomers up to the 40-mer, while Zn(2+) favors the formation of predominantly 3'-5' linked oligomers up to the 35-mer. When amounts of uracil, cytidine or adenosine 5'-phosphorimidazole equal to those of the guanosine derivative are included in the reaction mixture, the incorrect base is incorporated into the oligomer about 10% of the time with a Pb(2+) catalyst, but less than 0.5% of the time with Zn(2+). The Sn(2+), Sb(3+) and Bi(3+) ions are also found to promote the formation of 2'-5' oligomers, although not as effectively as Pb(2+), while no metal ions other than Zn(2+) promote the formation of the 3'-5' oligomers. The results may be important for the understanding of the evolution of nucleic acid replication in the absence of enzymes.

The dependence of shear modulus on dynamic relaxation and evolution of local structural heterogeneity in a metallic glass

International Nuclear Information System (INIS)

Huo, L.S.; Zeng, J.F.; Wang, W.H.; Liu, C.T.; Yang, Y.

2013-01-01

Starting from the nanoscale structural heterogeneities intrinsic to metallic glasses (MGs), here we show that there are two concurrent contributions to their microscale quasi-static shear modulus G I : one (μ) is related to the atomic bonding strength of solid-like regions and the other (G II ) to the change in the possible configurations of liquid-like regions (dynamic relaxation). Through carefully designed high-rate nanoscale indentation tests, a simple constitutive relation (μ = G I + G II ) is experimentally verified. On a fundamental level, our current work provides a structure–property correlation that may be applicable to a wide range of glassy materials

The role of surface and subsurface defects in the adsorption of oxygen and the adhesion of metals on TiO2(110)

DEFF Research Database (Denmark)

Salazar, Estephania Lira

2011-01-01

Titanium dioxide (TiO2) is a material of great technological importance due to its use in dye-sensitized solar cells, gas sensors, heterogeneous catalysis and photocatalysis. In the work described in this thesis, scanning tunneling microscopy (STM) was used to study fundamental processes occurring...

The Role of Electronic Excitations on Chemical Reaction Dynamics at Metal, Semiconductor and Nanoparticle Surfaces

Energy Technology Data Exchange (ETDEWEB)

Tully, John C. [Yale Univ., New Haven, CT (United States)

2017-06-10

Chemical reactions are often facilitated and steered when carried out on solid surfaces, essential for applications such as heterogeneous catalysis, solar energy conversion, corrosion, materials processing, and many others. A critical factor that can determine the rates and pathways of chemical reactions at surfaces is the efficiency and specificity of energy transfer; how fast does energy move around and where does it go? For reactions on insulator surfaces energy transfer generally moves in and out of vibrations of the adsorbed molecule and the underlying substrate. By contrast, on metal surfaces, metallic nanoparticles and semiconductors, another pathway for energy flow opens up, excitation and de-excitation of electrons. This so-called “nonadiabatic” mechanism often dominates the transfer of energy and can directly impact the course of a chemical reaction. Conventional computational methods such as molecular dynamics simulation do not account for this nonadiabatic behavior. The current DOE-BES funded project has focused on developing the underlying theoretical foundation and the computational methodology for the prediction of nonadiabatic chemical reaction dynamics at surfaces. The research has successfully opened up new methodology and new applications for molecular simulation. In particular, over the last three years, the “Electronic Friction” theory, pioneered by the PI, has now been developed into a stable and accurate computational method that is sufficiently practical to allow first principles “on-the-fly” simulation of chemical reaction dynamics at metal surfaces.

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...

Supported phosphate and carbonate salts for heterogeneous catalysis of triglycerides to fatty acid methyl esters

Science.gov (United States)

Britton, Stephanie Lynne

Fatty acid methyl esters made from vegetable oil, or biodiesel, have been identified as a substitute for diesel derived from crude oil. Biodiesel is currently made using a homogeneous base catalyst to perform the transesterification of triglycerides with methanol to generate fatty acid methyl esters (FAME). The use of a homogeneous catalyst necessitates additional purification of the product and byproducts before sale, and the catalyst is consumed and discarded. The development of a heterogeneous basic catalyst for the production of FAME is desirable. Tribasic phosphate salts and dibasic carbonate salts are active for the production of FAME but generally operate as homogeneous catalysts. Supporting these phosphate and carbonate salts on mesoporous MCM-41, microporous silica gel, and nonporous a-alumina proved successful to greater or lesser degrees depending on the identity of the support and pretreatment of the support. Although these salts were supported and were active for the production of FAME from canola oil, they proved to be operating as homogeneous catalysts due to leaching of the active species off the surface of the support. Further investigation of the active species present in the tribasic phosphate catalysts identified the active support as orthophosphate, and NMR studies revealed the phosphorus to be present as orthophosphate and diphosphate in varying proportions in each catalyst. Evaluation of the acid-washing support pretreatment process revealed that the exposure of the support to acid plays a large role in the development of activity on the surface of the catalyst, but manipulation of these parameters did not prevent leaching of the active site off the surface of the catalyst. Alternate methods of support pretreatment were no more effective in preventing leaching. Tribasic phosphate supported on silica gel is not effective as a heterogeneous catalyst for FAME production from triglycerides because of the lack of stability of the phosphate on the

Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts.

Science.gov (United States)

Wang, Hongliang; Wang, Huamin; Kuhn, Eric; Tucker, Melvin P; Yang, Bin

2018-01-10

Super Lewis acids containing the triflate anion [e.g., Hf(OTf) 4 , Ln(OTf) 3 , In(OTf) 3 , Al(OTf) 3 ] and noble metal catalysts (e.g., Ru/C, Ru/Al 2 O 3 ) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage through selective bonding to etheric oxygens while the noble metal catalyzed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf) 4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt % of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates by protonating hydroxyl groups and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote deoxygenation reactions catalyzed by super Lewis acids. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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...

Argilas pilarizadas - uma introdução An introduction to pillared clays

Directory of Open Access Journals (Sweden)

Fernando J. Luna

1999-02-01

Full Text Available The synthesis, characterization and some applications in catalysis of pillared clays are described at an introductory level. The use of x-ray diffraction, surface area measurements, thermal analysis, IR spectrophotometry and solid-state NMR in the characterization of pillared clays is briefly discussed. Pillarization followed by doping or introduction of metal clusters into clays could lead to the development of selective heterogeneous catalysts.

The phosphorus and the transition metals chemistry

International Nuclear Information System (INIS)

Mathey, F.

1988-01-01

The 1988 progress report, concerning the Polytechnic School unit (France), which studies the phosphorus and the transition metals chemistry, is presented. The laboratory activities are related to the following topics: the phosporus heterocyclic chemistry, the phosphorus-carbon double bonds chemistry, the new transition metals phosphorus compounds, the phosphonates and their uses. Some practical applications of homogeneous catalysis and new materials synthesis are investigated. The main results obtained are: the discovery of the tetra-phosphafulvalenes, the utilization of a new synthesis method of the phosphorus-carbon double bonds and the stabilization of the α-phosphonyled carbanions by the lithium diisopropylamidourea. The papers, the congress communications and the thesis are also shown [fr

Nanoscale chirality in metal and semiconductor nanoparticles.

Science.gov (United States)

Kumar, Jatish; Thomas, K George; Liz-Marzán, Luis M

2016-10-18

The field of chirality has recently seen a rejuvenation due to the observation of chirality in inorganic nanomaterials. The advancements in understanding the origin of nanoscale chirality and the potential applications of chiroptical nanomaterials in the areas of optics, catalysis and biosensing, among others, have opened up new avenues toward new concepts and design of novel materials. In this article, we review the concept of nanoscale chirality in metal nanoclusters and semiconductor quantum dots, then focus on recent experimental and theoretical advances in chiral metal nanoparticles and plasmonic chirality. Selected examples of potential applications and an outlook on the research on chiral nanomaterials are additionally provided.

Polymer-supported metals and metal oxide nanoparticles: synthesis, characterization, and applications

International Nuclear Information System (INIS)

Sarkar, Sudipta; Guibal, E.; Quignard, F.; SenGupta, A. K.

2012-01-01

Metal and metal oxide nanoparticles exhibit unique properties in regard to sorption behaviors, magnetic activity, chemical reduction, ligand sequestration among others. To this end, attempts are being continuously made to take advantage of them in multitude of applications including separation, catalysis, environmental remediation, sensing, biomedical applications and others. However, metal and metal oxide nanoparticles lack chemical stability and mechanical strength. They exhibit extremely high pressure drop or head loss in fixed-bed column operation and are not suitable for any flow-through systems. Also, nanoparticles tend to aggregate; this phenomenon reduces their high surface area to volume ratio and subsequently reduces effectiveness. By appropriately dispersing metal and metal oxide nanoparticles into synthetic and naturally occurring polymers, many of the shortcomings can be overcome without compromising the parent properties of the nanoparticles. Furthermore, the appropriate choice of the polymer host with specific functional groups may even lead to the enhancement of the properties of nanoparticles. The synthesis of hybrid materials involves two broad pathways: dispersing the nanoparticles (i) within pre-formed or commercially available polymers; and (ii) during the polymerization process. This review presents a broad coverage of nanoparticles and polymeric/biopolymeric host materials and the resulting properties of the hybrid composites. In addition, the review discusses the role of the Donnan membrane effect exerted by the host functionalized polymer in harnessing the desirable properties of metal and metal oxide nanoparticles for intended applications.

Modificação de zeólitas para uso em catálise Modifying zeolites for use in catalysis

Directory of Open Access Journals (Sweden)

Fernando J. Luna

2001-12-01

Full Text Available The use of zeolites and other molecular sieves as catalysts is discussed at an introductory level. The text includes a brief historic background on the use of zeolites in catalysis, and a discussion of some chemical and physical properties of silicalite, aluminosilicate, and aluminophosphate molecular sieves. The strategies currently used to chemically modify zeolites and related materials to produce catalysts with increased activity and selectivity are discussed, including the use of redox molecular sieves for hydrocarbon oxidation and the leaching of the active metals from the support.

Applications of UV/Vis Spectroscopy in Characterization and Catalytic Activity of Noble Metal Nanoparticles Fabricated in Responsive Polymer Microgels: A Review.

Science.gov (United States)

Begum, Robina; Farooqi, Zahoor H; Naseem, Khalida; Ali, Faisal; Batool, Madeeha; Xiao, Jianliang; Irfan, Ahmad

2018-11-02

Noble metal nanoparticles loaded smart polymer microgels have gained much attention due to fascinating combination of their properties in a single system. These hybrid systems have been extensively used in biomedicines, photonics, and catalysis. Hybrid microgels are characterized by using various techniques but UV/Vis spectroscopy is an easily available technique for characterization of noble metal nanoparticles loaded microgels. This technique is widely used for determination of size and shape of metal nanoparticles. The tuning of optical properties of noble metal nanoparticles under various stimuli can be studied using UV/Vis spectroscopic method. Time course UV/Vis spectroscopy can also be used to monitor the kinetics of swelling and deswelling of microgels and hybrid microgels. Growth of metal nanoparticles in polymeric network or growth of polymeric network around metal nanoparticle core can be studied by using UV/Vis spectroscopy. This technique can also be used for investigation of various applications of hybrid materials in catalysis, photonics, and sensing. This tutorial review describes the uses of UV/Vis spectroscopy in characterization and catalytic applications of responsive hybrid microgels with respect to recent research progress in this area.

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

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.

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.

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.

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

Assessment of research needs for advanced heterogeneous catalysts for energy applications. Final report: Volume 1, Executive summary

Energy Technology Data Exchange (ETDEWEB)

Mills, G.A.

1994-04-01

This report assesses the direction, technical content, and priority of research needs judged to provide the best chance of yielding new and improved heterogeneous catalysts for energy-related applications over a period of 5--20 years. It addresses issues of energy conservation, alternate fuels and feedstocks, and the economics and applications that could alleviate pollution from energy processes. Recommended goals are defined in 3 major, closely linked research thrusts: catalytic science, environmental protection by catalysis, and industrial catalytic applications. This volume provides a comprehensive executive summary, including research recommendations.

Chemical Bond Energies of 3d Transition Metals Studied by Density Functional Theory

DEFF Research Database (Denmark)

Moltved, Klaus A.d; Kepp, Kasper P.

2018-01-01

Despite their vast importance to inorganic chemistry, materials science and catalysis, the accuracy of modelling the formation or cleavage of metal-ligand (M-L) bonds depends greatly on the chosen functional and the type of bond in a way that is not systematically understood. In order to approach...

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.

Molecular Active Sites in Heterogeneous Ir-La/C-Catalyzed Carbonylation of Methanol to Acetates.

Science.gov (United States)

Kwak, Ja Hun; Dagle, Robert; Tustin, Gerald C; Zoeller, Joseph R; Allard, Lawrence F; Wang, Yong

2014-02-06

We report that when Ir and La halides are deposited on carbon, exposure to CO spontaneously generates a discrete molecular heterobimetallic structure, containing an Ir-La covalent bond that acts as a highly active, selective, and stable heterogeneous catalyst for the carbonylation of methanol to produce acetic acid. This catalyst exhibits a very high productivity of ∼1.5 mol acetyl/mol Ir·s with >99% selectivity to acetyl (acetic acid and methyl acetate) without detectable loss in activity or selectivity for more than 1 month of continuous operation. The enhanced activity can be mechanistically rationalized by the presence of La within the ligand sphere of the discrete molecular Ir-La heterobimetallic structure, which acts as a Lewis acid to accelerate the normally rate-limiting CO insertion in Ir-catalyzed carbonylation. Similar approaches may provide opportunities for attaining molecular (single site) behavior similar to homogeneous catalysis on heterogeneous surfaces for other industrial applications.

Genetic Manipulation of Outer Membrane Permeability: Generating Porous Heterogeneous Catalyst Analogs in Escherichia coli

Energy Technology Data Exchange (ETDEWEB)

Patel, TN; Park, AHA; Bantat, S

2014-12-01

The limited permeability of the E. coli outer membrane can significantly hinder whole-cell biocatalyst performance. In this study, the SARS coronavirus small envelope protein (SCVE) was expressed in E. coli cells previously engineered for periplasmic expression of carbonic anhydrase (CA) activity. This maneuver increased small molecule uptake by the cells, resulting in increased apparent CA activity of the biocatalysts. The enhancements in activity were quantified using methods developed for traditional heterogeneous catalysis. The expression of the SCVE protein was found to significantly reduce the Thiele moduli (phi), as well as increase the effectiveness factors (eta), effective diffusivities (D-e), and permeabilities (P) of the biocatalysts. These catalytic improvements translated into superior performance of the biocatalysts for the precipitation of calcium carbonate from solution which is an attractive strategy for long-term sequestration of captured carbon dioxide. Overall, these results demonstrate that synthetic biology approaches can be used to enhance heterogeneous catalysts incorporated into microbial whole-cell scaffolds.

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.

Application of Mössbauer spectroscopy in industrial heterogeneous catalysis: effect of oxidant on FePO{sub 4} material phase transformations in direct methanol synthesis from methane

Energy Technology Data Exchange (ETDEWEB)

Dasireddy, Venkata D. B. C., E-mail: dasireddy@ki.si [National Institute of Chemistry, Department of Catalysis and Chemical Reaction Engineering (Slovenia); Khan, Faiza B. [Energy Technology (South Africa); Hanzel, Darko [Jozef Stefan Institute (Slovenia); Bharuth-Ram, Krish [Durban University of Technology, Physics Department (South Africa); Likozar, Blaž [National Institute of Chemistry, Department of Catalysis and Chemical Reaction Engineering (Slovenia)

2017-11-15

The effect of the FePO{sub 4} material phase transformation in the direct selective oxidation of methane to methanol was studied using various oxidants, i.e. O{sub 2}, H{sub 2}O and N{sub 2}O. The phases of the heterogeneous catalyst applied, before and after the reactions, were characterized by M¨ossbauer spectroscopy. The main reaction products were methanol, carbon monoxide and carbon dioxide, whereas formaldehyde was produced in rather minute amounts. The Mössbauer spectra showed the change of the initial catalyst material, FePO{sub 4} (tridymite-like phase (tdm)), to the reduced metal form, iron(II) pyrophosphate, Fe{sub 2}P{sub 2}O{sub 7}, and thereafter, the material phase change was governed by the oxidation with individual oxidizing species.Mössbauer spectroscopy measurements applied along with X-ray diffraction (XRD) studies on fresh, reduced and spent catalytic materials demonstrated a transformation of the catalyst to a mixture of phases which depended on operating process conditions. Generally, activity was low and should be a subject of further material optimization and engineering, while the selectivity towards methanol at low temperatures applied was adequate. The proceeding redox mechanism should thus play a key role in catalytic material design, while the advantage of iron-based heterogeneous catalysts primarily lies in them being comparably inexpensive and comprising non-critical raw materials only.

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.

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

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 of metal-clay intercalation compound in the low temperature coal hydrogasification

Energy Technology Data Exchange (ETDEWEB)

Fuda, Kiyoshi; Kimura, Mitsuhiko; Miyamoto, Norimitsu; Matsunaga, Toshiaki

1986-10-23

Focusing the hydrogenating methanation by gaseous phase catalytic reactions of low temperature volatile components, the catalytic effects of Ni metal and the effects of carriers having sensitive effects on the catalytic activities of Ni metal were studied. Sample coals were prepared from Shin-Yubari coal, and Ni hydride-montmorillonite complex catalysts and the catalysts produced by carring Ni nitrate on alumina and burning in hydrogen gas flows were prepared. The hydrogasification were carried out in a reaction tube. As a result, the montmorillonite-Ni compounds catalysts had high catalitic effects and high conversion ratio of 90% or more in the low temperature coal gasification. The catalitic effects of carried Ni metal strongly depended on the carrier substances, and the rank of effects for the carriers was montmorillonite>zeorite>TiO/sub 2/>alpha-Al/sub 2/O/sub 3/>MgO>SiO/sub 2/=gamma-Al/sub 2/O/sub 3/. (3 figs, 3 tabs, 3 refs)

Enhancement of Bacterial Transport in Aerobic and Anaerobic Environments: Assessing the Effect of Metal Oxide Chemical Heterogeneities

International Nuclear Information System (INIS)

T.C. Onstott

2005-01-01

The goal of our research was to understand the fundamental processes that control microbial transport in physically and chemically heterogeneous aquifers and from this enhanced understanding determine the requirements for successful, field-scale delivery of microorganisms to metal contaminated subsurface sites. Our specific research goals were to determine; (1) the circumstances under which the preferential adsorption of bacteria to Fe, Mn, and Al oxyhydroxides influences field-scale bacterial transport, (2) the extent to which the adhesion properties of bacterial cells affect field-scale bacterial transport, (3) whether microbial Fe(III) reduction can enhance field-scale transport of Fe reducing bacteria (IRB) and other microorganisms and (4) the effect of field-scale physical and chemical heterogeneity on all three processes. Some of the spin-offs from this basic research that can improve biostimulation and bioaugmentation remediation efforts at contaminated DOE sites have included; (1) new bacterial tracking tools for viable bacteria; (2) an integrated protocol which combines subsurface characterization, laboratory-scale experimentation, and scale-up techniques to accurately predict field-scale bacterial transport; and (3) innovative and inexpensive field equipment and methods that can be employed to enhance Fe(III) reduction and microbial transport and to target microbial deposition under both aerobic and anaerobic conditions

Simple preparation of tungsten supported carbon nanoreactors for specific applications: Adsorption, catalysis and electrochemical activity

Energy Technology Data Exchange (ETDEWEB)

Mayani, Vishal J.; Mayani, Suranjana V.; Kim, Sang Wook, E-mail: swkim@dongguk.ac.kr

2015-08-01

Graphical abstract: - Highlights: • Tungsten carbon composites have shown great recognition in catalysis and electrochemistry. • W-carbon composites are prepared by template replication and W-doping on carbon cage. • Nanocomposites offer enormous assurance as adsorbent, electrode and heterogeneous catalyst. - Abstract: Porous carbon supported tungsten carbide nanoreactors, two sizes (∼25 and 170 nm), were designed using economical petroleum pitch residue followed by tungsten (W) doping. X-ray diffractions showed both carbon tungsten composites (CTC-25 and CTC-170) contained tungsten subcarbide (W{sub 2}C) and monocarbide (WC) as the major and minor crystalline phases, respectively. The present study provides a multiple perspective of carbon tungsten composites (CTCs) for methanol oxidation (as an electrode), adsorption (as an adsorbent) and degradation (as a solid catalyst) of methylene blue (MB). The operational electrodes were designed from both CTCs and used as a catalyst in an electrocatalysis process. The electrocatalysts exhibited high and stable catalytic performance (CTCE-25 > CTCE-170) in methanol electro-oxidation. The newly synthesized W-doped carbon nanoreactors were used successfully as an adsorbent for MB and a heterogeneous catalyst for MB oxidation. Ordered CTC-25 and CTC-170 exhibited dynamic MB adsorption within 15 min and complete oxidation of MB in 25–40 min. A synergetic effect between tungsten carbide and the carbon cage framework was noted.

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.

High-throughput heterogeneous catalyst research

Science.gov (United States)

Turner, Howard W.; Volpe, Anthony F., Jr.; Weinberg, W. H.

2009-06-01

With the discovery of abundant and low cost crude oil in the early 1900's came the need to create efficient conversion processes to produce low cost fuels and basic chemicals. Enormous investment over the last century has led to the development of a set of highly efficient catalytic processes which define the modern oil refinery and which produce most of the raw materials and fuels used in modern society. Process evolution and development has led to a refining infrastructure that is both dominated and enabled by modern heterogeneous catalyst technologies. Refineries and chemical manufacturers are currently under intense pressure to improve efficiency, adapt to increasingly disadvantaged feedstocks including biomass, lower their environmental footprint, and continue to deliver their products at low cost. This pressure creates a demand for new and more robust catalyst systems and processes that can accommodate them. Traditional methods of catalyst synthesis and testing are slow and inefficient, particularly in heterogeneous systems where the structure of the active sites is typically complex and the reaction mechanism is at best ill-defined. While theoretical modeling and a growing understanding of fundamental surface science help guide the chemist in designing and synthesizing targets, even in the most well understood areas of catalysis, the parameter space that one needs to explore experimentally is vast. The result is that the chemist using traditional methods must navigate a complex and unpredictable diversity space with a limited data set to make discoveries or to optimize known systems. We describe here a mature set of synthesis and screening technologies that together form a workflow that breaks this traditional paradigm and allows for rapid and efficient heterogeneous catalyst discovery and optimization. We exemplify the power of these new technologies by describing their use in the development and commercialization of a novel catalyst for the

Nanoporous gold membranes: From morphological control to fuel cell catalysis

Science.gov (United States)

Ding, Yi

Porous noble metals are particularly attractive for scientific research and industrial applications such as catalysis, sensing, and filtration. In this thesis, I will discuss the fabrication, characterization, and application of a new class of porous metals, called nanoporous metals (NPM). NPM is made during selective dissolution (also called dealloying) of reactive components (e.g., silver) from multi-component alloys (e.g., Ag/Au alloy). Commercially available white gold leaf (Ag65Au35) can, for example, be etched into nanoporous gold (NPG) membrane by simply floating the leaf on concentrated nitric acid for periods of a few minutes. NPG leaf adopts a single crystal porous structure within individual grains. The microstructure of NPG, such as the pore size, is tunable between a few nanometers to sub-micron length scale by either thermal annealing or post-treatment in nitric acid for extended period of time. A new gas-liquid-solid interface electroless plating technique is developed to uniformly cover the NPG surface with other metals, such as silver and platinum. This technique allows new opportunities of making functionalized nanostructures. We show that a combination of silver plating and dealloying can be used to make multimodal porous metals, which are expected to have application in sensing field. Electroless platinum plating onto NPG shows very usual growth mode. TEM observation indicates that the platinum layer on NPG surface takes a novel form of layer-islanding growth (Stranski-Krastanov growth). Annealing the Pt/NPG composite smoothens the Pt islands and forms a 1 nm coherent Pt layer on the NPG backbone, possibly with dislocation formation at the Pt/Au interface. Furthermore, it was found that we could dissolve the gold away in aqueous gold etchant, leaving behind the 1 nm-thick Pt shell, a structure we call nanotubular mesoporous platinum (NMP). Pt plated NPG has a series of unique structural properties, such as high active surface area, thermally

Metal-Organic Framework Nanosheets for Fast-Response and Highly Sensitive Luminescent Sensing of Fe3+

DEFF Research Database (Denmark)

Xu, Hui; Iversen, Bo Brummerstedt

of graphene, Since the discovery of graphene, series of two-dimensional (2-D) nanosheets materials such as metal oxides, metal hydroxides, transition metal chalcogenides (TMDs), boron nitride (BN) and black phosphorus have been of great interests, and have been extensively investigated for applications...... in electronics, lithium-ion batteries, catalysis and mechanical properties, etc. 2-D MOF nanosheets materials, as a new member of the 2-D nanomaterials family, are still at the very early stage. However, to the best of our knowledge, the 2-D MOF nanosheets materials for luminescent sensing have been rarely...

Highly stable noble-metal nanoparticles in tetraalkylphosphonium ionic liquids for in situ catalysis.

Science.gov (United States)

Banerjee, Abhinandan; Theron, Robin; Scott, Robert W J

2012-01-09

Gold and palladium nanoparticles were prepared by lithium borohydride reduction of the metal salt precursors in tetraalkylphosphonium halide ionic liquids in the absence of any organic solvents or external nanoparticle stabilizers. These colloidal suspensions remained stable and showed no nanoparticle agglomeration over many months. A combination of electrostatic interactions between the coordinatively unsaturated metal nanoparticle surface and the ionic-liquid anions, bolstered by steric protection offered by the bulky alkylated phosphonium cations, is likely to be the reason behind such stabilization. The halide anion strongly absorbs to the nanoparticle surface, leading to exceptional nanoparticle stability in halide ionic liquids; other tetraalkylphosphonium ionic liquids with non-coordinating anions, such as tosylate and hexafluorophosphate, show considerably lower affinities towards the stabilization of nanoparticles. Palladium nanoparticles stabilized in the tetraalkylphosphonium halide ionic liquid were stable, efficient, and recyclable catalysts for a variety of hydrogenation reactions at ambient pressures with sustained activity. Aerial oxidation of the metal nanoparticles occurred over time and was readily reversed by re-reduction of oxidized metal salts. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Metal and hydrogen catalysis in isotopic hydrogen exchange in some biologically important heterocyclic compounds

International Nuclear Information System (INIS)

Buncel, E.; Joly, H.A.; Jones, J.R.; Onyido, I.

1989-01-01

This study reports on the catalytic roles of metal and hydrogen ions in tritium exchange in some heterocyclic substrates which occur as residues in many biologically important molecules. We have found that detritiation of 1-methyl[2- 3 H]imidazole is inhibited by a number of metal ions. As well, inhibition of exchange rates was noted with Ag(I) and Cu(II) for [2- 3 H]thiazole and 1-methyl[8- 3 H]inosine, with Ag(I) for [2- 3 H]benzothiazole, and with Cu(II) for 1-methyl[8- 3 H]guanosine. A complete mechanistic description, which includes the various metal ion-coordinated species generated under the experimental conditions, is presented. The results demonstrate the reactivity order: protonated >> metal-coordinated >> neutral substrates. The differential catalytic effects of metal and hydrogen ions in these processes are discussed in terms of the extent of charge developed on the ligating heteroatom in the reaction intermediate. (author). 13 refs.; 1 fig

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.

Luminescent Metal Nanoclusters for Potential Chemosensor Applications

Directory of Open Access Journals (Sweden)

Muthaiah Shellaiah

2017-12-01

Full Text Available Studies of metal nanocluster (M-NCs-based sensors for specific analyte detection have achieved significant progress in recent decades. Ultra-small-size (<2 nm M-NCs consist of several to a few hundred metal atoms and exhibit extraordinary physical and chemical properties. Similar to organic molecules, M-NCs display absorption and emission properties via electronic transitions between energy levels upon interaction with light. As such, researchers tend to apply M-NCs in diverse fields, such as in chemosensors, biological imaging, catalysis, and environmental and electronic devices. Chemo- and bio-sensory uses have been extensively explored with luminescent NCs of Au, Ag, Cu, and Pt as potential sensory materials. Luminescent bi-metallic NCs, such as Au-Ag, Au-Cu, Au-Pd, and Au-Pt have also been used as probes in chemosensory investigations. Both metallic and bi-metallic NCs have been utilized to detect various analytes, such as metal ions, anions, biomolecules, proteins, acidity or alkalinity of a solution (pH, and nucleic acids, at diverse detection ranges and limits. In this review, we have summarized the chemosensory applications of luminescent M-NCs and bi-metallic NCs.

Spatial and seasonal heterogeneity of atmospheric particles induced reactive oxygen species in urban areas and the role of water-soluble metals

International Nuclear Information System (INIS)

Gali, Nirmal Kumar; Yang, Fenhuan; Jiang, Sabrina Yanan; Chan, Ka Lok; Sun, Li; Ho, Kin-fai; Ning, Zhi

2015-01-01

Adverse health effects are associated with exposure to atmospheric particulate matter (PM), which carry various chemical constituents and induce both exogenous and endogenous oxidative stress. This study investigated the spatial and seasonal variability of PM-induced ROS at four sites with different characteristics in Hong Kong. Cytotoxicity, exogenous and endogenous ROS was determined on a dose and time dependent analysis. Large spatial variation of ROS was observed with fine PM at urban site showing highest ROS levels while coarse PM at traffic site ranks the top. No consistent seasonal difference was observed for ROS levels among all sites. The highly heterogeneous distribution of PM-induced ROS demonstrates the differential capability of PM to produce oxidative stress, and the need to use appropriate metrics as surrogates of exposure instead of PM mass in epidemiologic studies. Several transition metals were found associated with ROS by different degree illustrating the complexity of mechanisms involved. - Highlights: • Adverse health effects are associated with size segregated atmospheric PM. • Seasonal and spatial variability of PM induced ROS determined in Hong Kong city. • Coarse PM ranks top in ROS generation on per volume and mass basis. • Traffic site demonstrated as source of potent inducer of cell toxicity. • No consistent seasonal difference observed for fine and coarse PM. - Heterogeneous PM-induced ROS distribution was observed in a city. Several water-soluble metals were associated with the ROS generation but with different degree from different sites

Nitrogen doped carbon nanotubes : synthesis, characterization and catalysis

NARCIS (Netherlands)

van Dommele, S.

2008-01-01