Download or read book Synthesis and Characterization of Cluster Derived Supported Bimetallic Catalysts written by and published by . This book was released on 2008 with total page 26 pages. Available in PDF, EPUB and Kindle. Book excerpt: New procedures have been developed for synthesizing di- and tri-metallic cluster complexes. The chemical properties of the new complexes have been investigated, particularly toward the activation of molecular hydrogen. These complexes were then converted into bi- and tri-metallic nanoparticles on silica and alumina supports. These nanoparticles were characterized by electron microscopy and were then tested for their ability to produce catalytic hydrogenation of unsaturated hydrocarbons and for the preferential oxidation of CO in the presence of hydrogen. The bi- and tri-metallic nanoparticles exhibited far superior activity and selectivity as hydrogenation catalysts when compared to the individual metallic components. It was found that the addition of tin greatly improved the selectivity of the catalysts for the hydrogenation of polyolefins. The addition of iron improves the catalysts for the selective oxidation of CO by platinum in the presence of hydrogen. The observations should lead to the development of lower cost routes to molecules that can be used to produce polymers and plastics for use by the general public and for procedures to purify hydrogen for use as an alternative energy in the hydrogen economy of the future.

Download or read book Synthesis and Characterization of Bimetallic Cluster derived Pt Au Catalysts and Au Supported on Mesoporous Supports written by Lorna Beatriz Ortiz-Soto and published by . This book was released on 2005 with total page 318 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book The Preparation and Characterization of Highly Dispersed Supported Bimetallic Catalysts from Inorganic and Organometallic Molecular Precursors written by Bert Donald Chandler and published by . This book was released on 1999 with total page 576 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Supported Bimetallic Catalysts Derived from Platinum gold Phosphine Stabilized Cluster Compounds Their Preparation Characterization and Catalytic Activity written by Irina Vladimirovna Gubkina Graf and published by . This book was released on 1996 with total page 492 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Supported Mono and Bimetallic Complexes and Clusters written by Joseph David Kistler and published by . This book was released on 2014 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Site-isolated solid supported metal catalysts are important in industry and technology due to the cost efficiency to make and to recover and reuse them. These types of materials have catalytic properties similar to molecular complexes in solution while being easy to separate in heterogeneous catalytic reactions. The goal of this work was to synthesize supported metal complex catalysts while maintaining uniform catalytic sites. The syntheses were performed using precise glovebox and Schlenk techniques to achieve these highly uniform structures. These materials were then used to understand the relationship between structure of a catalytic site and the activity of the catalyst. This fundamental understanding of catalysts is important in advancing the field of catalysis. The structure of the catalysts were characterized using infrared (IR), extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) spectroscopies along with high angle annular dark field- scanning transmission electron microscopy (HAADF-STEM), with the HAADF-STEM work carried out by colleagues in other research groups. The catalytic activity of the catalysts was examined with gas chromatography (GC) and mass spectrometry (MS). The samples characterized in this work include complexes and clusters of second and third row transition metals supported on highly crystalline metal oxides. Specifically, there is a large focus in this work on supported rhodium complexes prepared from the organometallic precursor, Rh(C2H4)2(C5H7O2) and a pre-calcined magnesium oxide (MgO). This specific catalyst is important as not only is it active for olefin hydrogenation at mild temperatures but also there are reports of a unique surface mediated synthesis of uniform rhodium dimers, which are ideal for catalytic comparison of structures with different nuclearities. Reactivities of the MgO-supported rhodium complexes and dimers for carbon monoxide oxidation were investigated with the results showing the dimers were significantly more active for the reaction at 353 K. The stability of the dimers was tested in different reactive conditions with the results showing that under conditions with excess oxygen, the dimers are less stable and less active than under conditions with excess carbon monoxide.A bimetallic catalyst was synthesized on MgO incorporating rhodium and osmium using Rh(C2H4)2 (acac) and Os3(CO)12 as precursors. A unique synthesis method was developed to create a site-isolated segregated bimetallic catalyst with the osmium and rhodium sites acting independently of each other for ethylene hydrogenation at 298 K. The metals remained structurally segregated and catalytically independent even following reduction in H2 at 393 K. Zeolites, another class of highly crystalline supports, were studied to gain information on the support effects in catalysts. The analogous rhodium complexes as were synthesized on the MgO were synthesized on zeolite HY. These catalysts were tested to determine structural and catalytic stability under hydrogen, a reducing gas, and CO, a catalyst poison, with the results showing that, as compared to the complexes on zeolite HY, MgO-supported rhodium complexes form more uniform stable clusters under H2 and develop unique catalytic properties, selectivity for partial hydrogenation of dienes, when exposed to CO. Another zeolite, KLTL, was studied with supported platinum complexes synthesized from the salt precursor, Pt(NH3)4(NO3)2. This catalyst was oxidized at 633K to form supported single-atom platinum complexes. Both the as-prepared Pt(NH3)4 and oxidized PtOx complexes were analyzed structurally and studied as catalysts for CO oxidation. The oxidized platinum complexes proved to have significantly higher activity for CO oxidation at 423 K. Furthermore, HAADF-STEM was used to directly identify the locations of the platinum atoms in the pores of the zeolite before and after oxidative treatment, providing a method of ex-situ tracking of supported metal atoms.

Download or read book Bimetallic Nanoparticles written by Alexandra Marcela Landry and published by . This book was released on 2016 with total page 92 pages. Available in PDF, EPUB and Kindle. Book excerpt: Bimetallic nanoparticles can lead to catalysts with improved turnover rates and selectivities, but many synthetic protocols, such as impregnation or precipitation, typically form particles of non-uniform size and composition. Colloidal methods may be able to improve their uniformity, but often require reagents that poison catalytic surfaces (ex. S, B, P). Such compositional non-uniformity and ubiquitous impurities have prevented rigorous conclusions about the consequences of alloying on reactivity and selectivity. Herein, we describe a sequential galvanic displacement-reduction (GDR) colloidal synthesis method using precursors containing only C, H, O, and N, that leads to bimetallic AuPt and PtPd nanoparticles narrowly distributed in size and composition. Au3+ or Pt4+ precursors were added to monometallic Pt or Pd clusters, respectively, whose surface atoms are thermodynamically driven to reduce and deposit the solvated cations onto cluster surfaces due to the lower reduction potentials (E0) of the seed metal relative to the precursor cations (E0Au> E0Pt> E0Pd); oxidized Pt and Pd surface atoms subsequently return to cluster surfaces upon reduction by the solvent, a reductant (ethanol or ethylene glycol, respectively). Such methods have been previously used to synthesize AuPd clusters from Pd seed clusters. TEM micrographs confirm that initial seed cluster sizes increase monotonically with increasing Au3+ or Pt4+ content, with final bimetallic cluster dispersity values near unity indicating a narrow size distribution. UV visible spectroscopy of AuPt cluster suspensions show no plasmon resonance features characteristic of Au nano-sized surfaces, indicating the presence of Pt atoms at bimetallic surfaces, as expected for GDR processes. Elemental analysis by EDS confirmed the formation of strictly bimetallic particles with the mean composition of the synthesis mixture. The GDR model requires that bimetallic growth be proportional to the initial seed surface area, with the number of precursor atoms deposited per surface metal atom of the seed constant and independent of seed metal size. Elemental analysis using EDS supports this hypothesis for thermodynamically favorable alloys such as PtPd and AuPd, but not for AuPt, an unfavorable alloy. These differences appear to reflect the segregation of metals within AuPt clusters during synthesis, placing the metal with the lower surface energy, Au, at cluster surfaces, and decreasing the availability of Pt0 surface atoms for GDR. Consequently, autocatalytic Au3+ reduction on Au0 sites becomes a competitive Au3+ reduction pathway during the synthesis of AuPt clusters. Polymers such as polyvinylpyrrolidone (PVP)--which bind to metal surfaces during synthesis via charge-transfer interactions--were required in colloidal suspensions to prevent particle agglomeration in solution, but must be removed prior to catalysis. We show that after depositing clusters on SiO2, PVP can be removed from particle surfaces by post-synthetic treatments at mild temperatures (d"423 K) in reductants such as H2 and/or EtOH without significant particle agglomerations. Reductants compete with the polymer at the metal surface, thus breaking the polymer-metal bond. The absence of surface residues was confirmed by the similar cluster sizes derived from O2 chemisorption and TEM measurements. Larger cluster sizes and surfaces that chemisorb oxygen more weakly--such as Pt relative to Pd--were found to facilitate the removal of PVP from metal particles due to weaker metal-polymer bonds. The model catalytic materials prepared in this study are of both fundamental and practical interest to probe the effects of alloying. Using AuPd and AuPt, we investigate the consequences of alloying with Au on the reactivity of catalyst surfaces saturated with either chemisorbed CO* (CO oxidation) or O* (H2 oxidation) that bind strongly to Pt and Pd surfaces and inhibit rates. Singleton Pt-CO* bond energies, reflected in vibrational CO* stretches, were decoupled from dipole-dipole coupling effects using isotopic dilution methods, and were shown to decrease with increasing catalyst Au content. Despite lower CO* binding energies, CO oxidation turnover rates (normalized per metal surface atom) on AuPt catalysts decreased with increasing Au content. These results show that CO oxidation rates depend weakly on CO* binding energy--consistent with the reported structed insensivity of this reaction--and that Au acts primarily as an inert diluent of the active Pt ensembles required for catalysis. In contrast, H2 oxidation turnover rates (normalized per metal surface atom) on AuPt and AuPd catalysts increase with increasing Au content (up to 11 % at. Au content on AuPt and up to 67 % at. Au content on AuPd), indicating that the reactivity of O* saturated surfaces is more sensitive to changes in adsorbate binding energy than surfaces saturated in CO*, consisted with the reported structure sensitivity of reactions on O* saturated surfaces. Reconstruction of CO* adlayers is facile due to highly mobile CO* molecules, thus allowing CO* adlayers to access configurations that help mitigate strong CO* binding and introduce vacancies. O* adlayers, meanwhile, are more strongly bound to Pt and Pd metal surfaces and less mobile. H2 oxidation rates thus depend more strongly on adsorbate binding energy than CO oxidation rates.

Download or read book Directed Synthesis and Characterization of Supported Bimetallic Overlayer Catalysts written by Michael P. Latusek and published by . This book was released on 2008 with total page 240 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Bimetallic Catalysts written by John H. Sinfelt and published by Wiley-Interscience. This book was released on 1983-09-29 with total page 190 pages. Available in PDF, EPUB and Kindle. Book excerpt: Presents an account of the research on bimetallic catalysts. Focuses attention on the possibility of influencing the selectivity of chemical transformations on metal surfaces and preparing metal alloys in a highly dispersed state. Covers the validation and elucidation of the bimetallic cluster concept. Includes figures and tables.

Download or read book Metal Clusters in Catalysis written by Bruce C. Gates and published by Elsevier Publishing Company. This book was released on 1986 with total page 686 pages. Available in PDF, EPUB and Kindle. Book excerpt: Research on metal clusters (compounds with metal-metal bonds) has undergone explosive growth and the subject is now perhaps one of the hottest'' topics in organometallic chemistry. The prospect of catalytic applications has motivated a large part of the research mentioned in this book - the long term goal being to exploit the unique properties of metal clusters to prepare catalysts with new activities and selectivities. This is the first book to address the role of metal clusters in catalysis. The coverage is up-to-date and is particularly comprehensive, ranging from molecular chemistry of clusters (synthesis, structure, thermochemistry, reactivity, and homogeneous catalysis) to supported clusters (molecular analogues on polymers, and metal oxides and metals in zeolite cages). Preparation by methods of organometallic surface chemistry and metal atom chemistry and characterization of surface structures by physical methods are highlighted. Concepts unifying metal cluster chemistry and the chemistry of metal surfaces are elucidated. Of particular value to the user will be the cluster and subject indexes. The cluster index is organized in alphabetical order according to the metal.

Download or read book Structurally Well defined Supported Iridium Cluster Catalysts written by Ailian Zhao and published by . This book was released on 1996 with total page 436 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Catalyst Preparation written by John Regalbuto and published by CRC Press. This book was released on 2016-04-19 with total page 490 pages. Available in PDF, EPUB and Kindle. Book excerpt: This text explores the optimization of catalytic materials through traditional and novel methods of catalyst preparation, characterization, and monitoring for oxides, supported metals, zeolites, and heteropolyacids. It focuses on the synthesis of bulk materials and of heterogeneous materials, particularly at the nanoscale. The final chapters examine pretreatment, drying, finishing effects, and future applications involving catalyst preparation and the technological advances necessary for continued progress. Topics also include heat and mass transfer limitations, computation methods for predicting properties, and catalyst monitoring on laboratory and industrial scales.

Download or read book Supported Bimetallic Catalysts Derived from Molecular Metal Clusters written by Shiu-Lun Anthony Fung and published by . This book was released on 1989 with total page 714 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Metal Oxide supported Cluster Catalysts Derived from Organometallic Precursors written by Felix ShangChung Lai and published by . This book was released on 2003 with total page 1092 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Silica Supported Iron bimetallic Catalysts for the Fischer Tropsch Synthesis written by Jeffrey Allen Amelse and published by . This book was released on 1980 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Catalysis By Gold written by Geoffrey C Bond and published by World Scientific. This book was released on 2006-08-15 with total page 383 pages. Available in PDF, EPUB and Kindle. Book excerpt: Gold has traditionally been regarded as inactive as a catalytic metal. However, the advent of nanoparticulate gold on high surface area oxide supports has demonstrated its high catalytic activity in many chemical reactions. Gold is active as a heterogeneous catalyst in both gas and liquid phases, and complexes catalyse reactions homogeneously in solution. Many of the reactions being studied will lead to new application areas for catalysis by gold in pollution control, chemical processing, sensors and fuel cell technology. This book describes the properties of gold, the methods for preparing gold catalysts and ways to characterise and use them effectively in reactions. The reaction mechanisms and reasons for the high activities are discussed and the applications for gold catalysis considered./a

Download or read book Synthesis and Characterization of Innovative Catalysts for the Selective Oxidation of 5 hydroxymethylfurfural written by Danilo Bonincontro and published by . This book was released on 2019 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: The depletion of fossil-derived resources and the need to decrease the emission of green-house gases led scientists to look for sustainable materials to replace the already existing fossil-derived ones. For instance, 2,5-furandicarboxylic acid (FDCA) has been pointed out as the bioderived counterpart of terephthalic acid for the synthesis of polyesters. In fact, FDCA could be obtained by means of selective oxidation of 5-hydroxymethylfurfural (HMF), a bio-derived platform molecule produced by glucose hydrolysis. This reaction is known to be catalyzed by supported metal nanoparticle systems in presence of inorganic bases under batch conditions. This work deals with the development of catalytic systems able to perform the base-free HMF oxidation, since the possibility to circumvent base addition leads more sustainable processes. In particular, two different sets of catalytic systems have been studied: mono- and bimetallic Au and Pd nanoparticles on nano-sized NiO, and mono- and bimetallic Pt/Sn systems on titania, prepared via cluster precursor decomposition. Another topic that will be discussed in this thesis focuses on the development of catalytically active polymeric membranes obtained via electrospinning and their application as catalytic system for HMF oxidation either under basic and neutral aqueous conditions. In details, polyacrylonitrile and nylon have been tested as electrospun polymeric matrixes for the embedding of Au-based nanoparticles and Pt clusters.

Download or read book Synthesis Characterization and Performance of Supported Molecular Catalysts written by Erjia Guan and published by . This book was released on 2018 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Metals are dominant catalysts, being used in forms ranging from simple atomically dispersed (single-site) metal complexes to few-atom clusters to nanoparticles to bulk metals. Investigations of atomically dispersed metal complexes are drawing wide attention because their well-defined structures facilitate fundamental understanding of catalysis as well as offering new catalytic properties. In this work, we extend the field of atomically dispersed supported metal catalysts to dinuclear clusters to build a bridge between atomically dispersed metal complexes and few-atom clusters. Thus, the research extends the subject of atomically dispersed supported catalysts to supported metal pair-site catalysts, which have heretofore been little investigated because of their instability, lack of uniformity, and difficulty of precise synthesis. A separate, collaborative project reported on here includes characterization by in-situ X-ray absorption spectroscopy of the structures of single-site supported metals present as promoters in complex catalysts that contain metal nanoparticles for selective hydrogenation of nitroarenes. Iridium and rhodium pair-site catalysts supported on MgO were synthesized and characterized with infrared (IR) and X-ray absorption spectroscopies and high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM), supported by density functional theory (DFT) calculations done by collaborators. In-situ IR and X-ray absorption near edge structure (XANES) spectra were used to characterize the structural changes of the pair-sites under various treatment conditions, including ligand substitution reactions involving CO and hydrogen. Catalytic properties for ethylene hydrogenation and H-D exchange in the H2 + D2 reaction were tested and compared with those of single-site iridium and rhodium analogues as well as few-atom clusters of these metals supported on MgO. The pair-site catalysts on MgO activated by removal of ligands facilitate H2 dissociation much more rapidly than their single-site analogues and catalyze ethylene hydrogenation one to two orders of magnitude faster than their single-site analogues on MgO. The pair sites are active for ethylene hydrogenation even after being partially poisoned by CO, and, in contrast, the analogous single-site catalysts are fully poisoned. The results provide understanding of the roles of neighboring metal sites and the effects of ligands on pair sites catalysts, opening opportunities for synthesis of stable pairs of various metals on various supports. The benefits of such stable metal pair sites may extend to numerous reactions other than those investigated in this work. The single-site promoters investigated in this work are Sn cations on TiO2 supports that incorporate noble metal nanoparticle catalysts. These catalysts decidedly outperform the comparable unpromoted supported metals for hydrogenation of nitroarenes substituted with various reducible groups. X-ray absorption spectroscopy at the Sn K edge was used to characterize the structural changes in the single-site Sn in the catalysts as influenced by H2 and by nitrobenzene at 353 K and 1 atm. The changes in Sn–O coordination numbers and distances give evidence that the high activity and selectivity of these catalysts result from the creation of oxygen vacancies on the TiO2 surface associated with single-site Sn sites that lead to efficient, selective activation of the nitro group (in contrast to the other reducible group) coupled with reaction involving hydrogen atoms activated on the nearby metal nanoparticles.