Molecular Structure-reactivity Relationships for Supported Molybdenum Oxide Catalysts PDF Download

Author: Hangchun Hu
Publisher:
ISBN:
Category : Catalysts
Languages : en
Pages : 444

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Author:
Publisher:
ISBN:
Category :
Languages : en
Pages :

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Mixed Mo-V-Sb-Nb and Mo-V-Te-Nb oxides were recently discovered as highly active and selective catalysts for the propane oxidation to propylene and oxygenates, i.e. acrolein and acrylic acid. Fundamental information is needed for understanding the bulk and surface molecular structure-activity/selectivity relationships and providing rules of rational design of improved mixed metal oxide catalysts for the selective oxidation of propane. The phase composition and catalytic activity of the model Mo-V-Sb-Nb-O system strongly depended on the synthesis route and composition. A number of distinct solid-state phases were observed in this system: Mo6V9O40, MoO3, rutile SbVO4 and the defect "Mo-V-Nb-O" phases. The kinetic studies indicated that the high selectivity to acrylic acid (2̃0 mol.%) was associated with the Mo6V9O40 and the defect "Mo-V-Nb-O" phases. The synthesis of these mixed Mo-V-Sb-Nb-O system was performed using combinatorial chemistry techniques to explore the utility of liquid phase automated synthesis for the reproducible preparation of these catalysts. This study indicated good reproducibility of phase compositions and catalytic properties and provided new insights into the transformation processes that occur in these oxides with time on stream. It was discovered in this research that the model mixed Mo-V-Te-O catalyst represents a simple model system for elucidating the molecular structure-activity/selectivity relationships in propane selective oxidation. This catalyst contains the two major crystalline phases proposed as active and selective for propane oxidation. This research elucidated the effect of the chemical composition, solution pH and thermal treatment on phase composition and catalytic performance. High resolution TEM study established the crystal structures of the hexagonal and orthorhombic phases in terms of their space groups, unit cell parameters, atomic coordinates and elemental compositions. In order to understand the role of the structure, morphology and composition of mixed Mo-V-Te-Nb-O system, novel synthesis approaches employing ordered arrays of colloidal polystyrene spheres (0.4 ưm) were successfully developed. These novel nanocrystalline catalysts with surface areas in the 80-110 m2/g range consisted of 20-50 nm particles of desirable catalytic phases and contained 6-20 nm pores. Kinetic studies demonstrated the acrylic acid yields exceeding 40 mol.% and approaching the commercial targets for the selective oxidation of propane to acrylic acid.

Author: Edward L. Lee
Publisher:
ISBN: 9780549277521
Category :
Languages : en
Pages : 289

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SiO2-supported metal oxide catalysts find a wide range of industrial applications, including oxidation, isomerization, metathesis, and polymerization reactions. Unfortunately, the fundamental understanding of these catalysts based on the structure---reactivity relationship is still lacking and not well understood. Therefore, resolving the molecular structure and the relationship with the catalytic reactivity is the motivation of this investigation.

Author: D.H.R. Barton
Publisher: Springer Science & Business Media
ISBN: 1461530008
Category : Science
Languages : en
Pages : 503

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This monograph consists of the proceedings of the Fifth International Symposium on the Activation of Dioxygen and Homogeneous Catalytic Oxidation, held in College Station, Texas, March 14-19, 1993. It contains an introductory chapter authored by Professors D. H. R. Barton and D. T. Sawyer, and twenty-nine chapters describing presentations by the plenary lecturers and invited speakers. One of the invited speakers, who could not submit a manuscript for reasons beyond his control, is represented by an abstract of his lecture. Also included are abstracts of forty-seven posters contributed by participants in the symposium. Readers who may wish to know more about the subjects presented in abstract form are invited to communicate directly with the authors of the abstracts. This is the fifth international symposium that has been held on this subject. The first was hosted by the CNRS, May 21-29, 1979, in Bendor, France (on the Island of Bandol). The second meeting was organized as a NATO workshop in Padova, Italy, June 24-27, 1984. This was followed by a meeting in Tsukuba, Japan, July 12-16, 1987. The fourth symposium was held at Balatonfured, Hungary, September 10-14, 1990. The sixth meeting is scheduled to take place in Delft, The Netherlands (late Spring, 1996); the organizer and host will be Professor R. A. Sheldon.

Author: Israel E. Wachs
Publisher: Momentum Press
ISBN: 1606501844
Category : Science
Languages : en
Pages : 220

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Heterogeneous catalysis has undergone a revolutionary change in the past two decades due to the development of sophisticated characterization methods that provide fundamental information about the catalyst bulk structures, surfaces, and their properties. For the first time, these characterization methods have allowed researchers to "see" the surfaces of catalytic materials, their bulk structures (crystalline as well as amorphous phases), the influence of the process conditions on the catalytic material, as well as the effect of different synthesis methods. This new information has tremendously advanced our understanding of catalytic materials and their properties. These characterization methods have become our "eyes" and are indispensible in the development of new catalytic materials. It is hard to conceive of a modern heterogeneous catalysis activity, be it research or manufacturing, without the aid of these new characterization techniques.

Author: H.H. Kung
Publisher: Elsevier
ISBN: 0080887422
Category : Science
Languages : en
Pages : 299

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In this book the author presents an up-to-date summary of existing information on the structure, electronic properties, chemistry and catalytic properties of transition metal oxides.The subjects covered in the book can be divided into three sections. The first (chapters 1 to 3) covers the structural, physical, magnetic, and electronic properties of transition metal oxides. Although the emphasis is on surface properties, relevant bulk properties are also discussed. The second section (chapters 4 to 7) covers surface chemical properties. It includes topics that describe the importance of surface coordinative unsaturation in adsorption, the formation of surface acidity and the role of acidity in determining surface chemical properties, the nature and reactivities of adsorbed oxygen, and the surface chemistry in the reduction of oxides. The third section (chapters 8 to 14) is on the catalytic properties. Various catalytic reactions including decomposition, hydrogenation, isomerization, metathesis, selective oxidation, and reactions involving carbon oxides are discussed. Emphasis is placed more on reaction mechanisms and the role of catalysts than on kinetics and processes. Chapters on the preparation of oxide catalysts and on photo-assisted processes are also included. Whenever appropriate, relationships between various topics are indicated.Written for surface physicists, chemists, and catalytic engineers, the book will serve as a useful source of information for investigators and as a comprehensive overview of the subject for graduate students.

Author: Israel E. Wachs
Publisher: Springer Nature
ISBN: 3031071255
Category : Technology & Engineering
Languages : en
Pages : 1109

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Co-edited by world-renowned scientists in the field of catalysis, this book contains the cutting-edge in situ and operando spectroscopy characterization techniques operating under reaction conditions to determine a materials’ bulk, surface, and solution complex and their applications in the field of catalysis with emphasis on solid catalysts in powder form since such catalyst are relevant for industrial applications. The handbook covers from widely-used to cutting-edge techniques. The handbook is written for a broad audience of students and professionals who want to pursue the full capabilities available by the current state-of-the-art in characterization to fully understand how their catalysts really operate and guide the rational design of advanced catalysts. Individuals involved in catalysis research will be interested in this handbook because it contains a catalogue of cutting-edge methods employed in characterization of catalysts. These techniques find wide use in applications such as petroleum refining, chemical manufacture, natural gas conversion, pollution control, transportation, power generation, pharmaceuticals and food processing. fdsfds

Author: Daniel Duprez
Publisher: World Scientific
ISBN: 1783263342
Category : Science
Languages : en
Pages : 1035

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This book offers a comprehensive overview of the most recent developments in both total oxidation and combustion and also in selective oxidation. For each topic, fundamental aspects are paralleled with industrial applications. The book covers oxidation catalysis, one of the major areas of industrial chemistry, outlining recent achievements, current challenges and future opportunities. One distinguishing feature of the book is the selection of arguments which are emblematic of current trends in the chemical industry, such as miniaturization, use of alternative, greener oxidants, and innovative systems for pollutant abatement. Topics outlined are described in terms of both catalyst and reaction chemistry, and also reactor and process technology.

Author: David Earl Huffman
Publisher:
ISBN:
Category : Molybdenum compounds
Languages : en
Pages : 334

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The cocondensation reactions of molybdenum trioxide vapor with tetraalkoxysilanes, trimethylalkoxysilanes, and hexamethyldisiloxane at -196°C were investigated. The products from the metal vapor reactions of tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane were characterized as molybdenum(VI)dioxodialkoxy compounds. The isolated compounds were found to be polymeric in the solid state by bridging through alkoxide groups. Metal vapor reaction of trimethylmethoxysilane gave an inseparable mixture of molybdenum(VI)alkoxysiloxy compounds which were also polymeric in nature. The metal vapor reactions of tetra-2-butoxysilane and trimethyl-t-butoxysilane gave butenes as a primary organic product and an uncharacterized blue molybdenum-containing solid. All products isolated in this study were sensitive to atmospheric moisture and light. The molybdenumdioxoalkoxy and molybdenumdioxoalkoxysiloxy compounds are good model compounds for the oxidation of alcohols. Decomposition studies of Mo(0)2(OMe)2 and Mo(0)2(OMe)x(OSiMe3)y yielded oxidation products of methanol, including dimethylether, formaldehyde, methyl formate, and dimethoxymethane. The reactivity of Mo(0)2(OEt)2 towards acidic protons was used to attach the molybdenum(VI)dioxo group to the surface of alumina (Al203), silica (Si02), titania (Ti02), zirconia (Zr02), and HY-zeolite. Chemical analysis and infrared spectroscopic studies indicate that dioxomolybdenum is attached to the support through bridging oxides between the support metal and molybdenum. The +2, +4, and +6 oxidation states of the surface attached molybdenum could be accessed by oxidation or reduction with 02 or H2, respectively. A survey of the catalytic nature for oxidation, metathesis, and Fischer- Tropsch synthesis of the supported molybdenum compounds in appropriate oxidation states was made. Dramatic differences in the activity and selectivity for oxidation of alcohols were observed depending on the support used. The Ti02 supported Mo(VI) showed the highest activity and selectivity for the oxidation of methanol to formaldehyde. The A1203 supported Mo(IV) system was the most active catalyst for propylene metathesis with the Si02 supported Mo(IV) system showing much less activity.

Author: Craig Wallace Colling
Publisher:
ISBN:
Category :
Languages : en
Pages : 304

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