Abstract: Publication date: 2013 Source:Advances in Catalysis, Volume 56 Author(s): Karl D. Hammond , Wm. Curtis Conner Jr. Heterogeneous catalysis usually takes place by sequences of reactions involving fluid-phase reagents and the exposed layer of the solid catalyst surface. Estimation of the total catalyst surface area, its potential accessibility to gas- or liquid-phase reactants, and general catalytic activity are initially based on the morphology of the catalyst. Universally, measurements of adsorption and their interpretation are used to estimate the surface area and porosity relevant to catalytic reactions. We provide here a description of many traditional and recent techniques in adsorption-based catalyst characterization intended for experimental practitioners of adsorption. Our chapter includes descriptions of which regions of the isotherm correspond to micropore filling, mesopore filling, surface coverage, and saturation, supplemented by discussions of model isotherms, from the Langmuir isotherm and the Brunauer–Emmett–Teller theory to the Halsey equation. Pore size distribution methods include the Barrett–Joyner–Halenda and related methods for mesopores, empirical methods developed for micropores, and simulation-based methods that have finally resolved the differences between adsorption (increasing loading) and desorption (decreasing loading). This chapter also includes a discussion of hysteresis and metastability, both of which “trip up” experimentalists from time to time. We finish with a description of data acquisition methods and equipment, which are often obscured behind the facade of automation, and a discussion of what users should be aware of and what can go wrong.
Abstract: Publication date: 2013 Source:Advances in Catalysis, Volume 56 Author(s): Robert Schlögl This review is concerned with nanoscale carbon as a catalyst. Elemental carbon has become available in many nanostructured forms representing combinations of the hybridizations found in fundamental carbon allotropes, and the materials can be enriched by a large number of surface functional groups, some generated by nanostructuring. Consequently, many examples of catalytic applications of carbon are documented, but the development of the field has been hampered by the lack of a conceptual approach linking structure and function and by the lack of understanding of synthesis of the materials. This chapter provides a foundation for an advanced comprehension of the catalytic reactivity of carbon and addresses key aspects of characterization and synthesis. The usefulness of X-ray diffraction, Raman spectroscopy, and electron microscopy for the characterization of nanoscale carbons is briefly contrasted with the limitations of these methods. The various structural elements—among them carbon hybridization, local defects, and topology—that contribute to the electronic structure are discussed in detail. The difficulties of analyzing the resulting complex electron spectra are highlighted. In its core part, this chapter uses the derived knowledge of the electronic structure to arrive at concepts illustrating carbon’s potential in catalysis. A general synthesis strategy for the controlled functionalization of carbons is laid out. The ambivalent role of carbon deposits on catalyst surfaces as poisons or an active phase is demonstrated. One-third of the chapter is devoted to two case studies that illustrate the ideas; the catalytic transformations are the oxidative dehydrogenation of ethylbenzene and of alkanes.
Abstract: Publication date: 2013 Source:Advances in Catalysis, Volume 56 Author(s): Tracy J. Benson , Prashant R. Daggolu , Rafael A. Hernandez , Shetian Liu , Mark G. White The composition of a typical pyrolysis oil is used to pose the problem of oxygen removal from this oil and to motivate a discussion of the different reactions for oxygen removal that are thermodynamically favored. From a consideration of this thermodynamics analysis of the favored reactions, the surface chemistry literature is surveyed to reveal those materials that allow the adsorption of oxygen-containing species. Included in this survey are experimental and theoretical studies. This consideration of adsorption of oxygen-containing species prompts a further examination of the literature of reaction mechanisms and reaction sequences to reveal the conventional pathways to remove oxygen from the substrates. Moreover, the literature of hydroprocessing is reviewed to show how traditional hydrodesulfurization catalysts have been studied as a hydrodeoxygenation (HDO) catalyst of the reactive species in pyrolysis oils. Furthermore, aqueous-phase reforming is discussed as an alternative to HDO.
Abstract: 2012 Publication year: 2012 Source:Advances in Catalysis, Volume 55
Gold can be deposited as nanoparticles (NPs) with diameters of 2–5nm and clusters with diameters less than 2nm on a variety of materials such as oxides, carbides, and sulfides of transition metals, carbons, and organic polymers. Such supported gold NPs and clusters exhibit surprisingly high catalytic activities for many reactions, with both gas- and liquid-phase reactants, in particular, at temperatures below 573K. Until now, more than 10 techniques have been developed for depositing gold as NPs and clusters. The atomic scale structures of supported NPs and clusters have been extensively and intensively investigated with a high-resolution transmission electron microscopy. The mechanisms of catalysis by supported gold NPs have recently been elucidated by using real powder catalysts and model single-crystal catalysts for the low-temperature oxidation of CO. Another simple reaction that has recently been investigated is dihydrogen dissociation, for which gold NP catalysts are still poorly active. Both of these reactions have been demonstrated to take place at perimeter interfaces around the gold NPs. This result means that there is a great chance for gold to exhibit high catalytic activity for hydrogenation reactions by an appropriate choice of metal oxide supports and by minimizing the diameters of gold particles. The catalytic nature of gold clusters has also been investigated theoretically in relation to the effect of cluster size and the influence of organic ligands and polymers. The catalytic performance of gold NPs and clusters has been explored extensively for reactions of both gases and liquids. Supported gold catalysts are useful for air cleaning at room temperature, and they are valuable for green production of bulk and fine chemicals. Supported gold clusters are expected to open new doors for simple chemistry for the selective manufacture of needed products. Size and structure specificity are expected to present opportunities for selective conversions. It is recommended that researchers explore the magic numbers and structures of gold and suitable support materials for selected target reactions.
Abstract: 2012 Publication year: 2012 Source:Advances in Catalysis, Volume 55
After their discovery in the early 1990s, ordered mesoporous materials have become one of the most widely investigated classes of materials, and applications have been considered in many areas, in particular in catalysis. They have attracted attention because of their unique properties such as high surface areas, controllable compositions, crystallinity, thermal and chemical stability, tailored porosities, narrow pore size distributions, concave surface curvatures, surface functionalities, as well as the opportunities they offer for incorporation of catalytically active and selective species. This chapter is focused on the properties of ordered mesoporous solids that distinguish them from more conventional porous catalytic materials. Emphasis is placed on history, development, and methods of synthesis of ordered mesoporous materials.
Abstract: 2011 Publication year: 2011 Source:Advances in Catalysis, Volume 54
One of the key challenges in catalysis is the generation of catalytically active metal centers that are highly Lewis acidic so that the metal center can easily bind with a nucleophilic monomer to initiate a catalytic process. With this goal in mind, we pursued the designed synthesis of catalytically active metal centers with enhanced Lewis acidity, adopting two different synthetic strategies. One is the introduction of oxygen between two different metal atoms, and the other is the chemical attachment of highly electronegative fluorine around the catalytically active metal center. The attachment of the oxygen between the two metal centers also brings the metals into close proximity at the molecular level, resulting in a pronounced chemical communication between the metals. The compounds with different metals have often modified the fundamental properties of the individual metal atoms through the well-known “cooperative interaction” that is otherwise difficult to achieve. The synthetic strategy takes advantage of the Brønsted acidic character of the M(OH) moiety in building up a new class of heterometallic complexes. Further, the discovery of Me3SnF as one of the most useful fluorinating reagents for organometallic complexes leads to the successful preparation of organometallic fluorides of Group-4 metals. This synthetic development has resulted in the availability of catalysts of a new class bearing enhanced Lewis acidic metal centers resulting either from oxygen bridging or from the attachment of a highly electronegative fluorine to a catalytically active metal center. In many cases, these complexes have proved to be excellent candidates for olefin polymerization, ring-opening polymerization of caprolactone, olefin epoxidation, and olefin hydroformylation. The improvement in the catalytic properties is a result of the presence of a more electrophilic metal center, which is essential for the catalysis.
Abstract: 2011 Publication year: 2011 Source:Advances in Catalysis, Volume 54
This chapter summarizes the main achievements in the area of supramolecular catalysis in the past decade. Supramolecular chemistry emerged 40 years ago. The initial focus was host–guest chemistry, and one target application was the use of such interactions to bring catalyst and substrate together. Examples in the first part of this chapter illustrate how rates of reactions, selectivities, regioselectivities, and enantioselectivities may change through assemblies designed as models for enzymes. In the beginning, natural host molecules such as cyclodextrins and modified cyclodextrins received most attention, but later a plethora of synthetic hosts were developed. More recently, the construction of host molecules was facilitated enormously by the introduction of supramolecular “tools”; according to this principle, large entities are constructed by bringing together smaller building blocks via noncovalent forces, such as hydrogen bonding, ionic bonding, metal–ligand coordination bonding, fluorophilic interactions, etc. A large number of host molecules were reported in the past decade, and most of them do not function merely as hosts but instead are containers that can host more than one molecule and have catalytic functions incorporated. A variety of names are used for these entities, such as capsule, cavitand, nanoreactor, nanocontainer, cage molecule, and receptor molecule. Large changes in selectivities and rates of catalytic reactions relative to those of bare catalytic sites have been reported. The second part of this chapter deals with the supramolecular construction of ligands or entire catalyst assemblies. This modular construction has enabled the synthesis of large catalyst libraries, which are useful for catalyst optimization and catalyst screening. In this way, new catalysts were developed, and new ways to control rates and selectivities of catalytic reactions were recognized. Biomacromolecules (and modified variants) have been used, particularly as sources of chirality in catalytic transformations, via supramolecular interactions with homogeneous catalysts. The last part of the chapter shows that supramolecular interactions can be used successfully for the immobilization of homogeneous catalysts. By its nature, the bonding is reversible, and the developments have led to a new reactor configuration for use of homogeneous catalysts, termed reverse-flow adsorption.
Abstract: 2011 Publication year: 2011 Source:Advances in Catalysis, Volume 54
Computational studies have recently generated important information regarding reaction intermediates and activation barriers of elementary reaction steps that are part of the Fischer–Tropsch synthesis. We use these results to analyze various mechanistic options that have been proposed for the Fischer–Tropsch synthesis. The computational results do not support the Pichler–Schulz chain-growth mechanism, which postulates chain growth by CO insertion. Rather, the results are in agreement with the Sachtler–Biloen mechanism, which postulates chain growth via adsorbed “C1” species; furthermore, the Gaube chain-growth mechanism, which closely resembles that proposed by Maitlis, is found to be preferred over the initially assumed Brady–Pettit mechanism. The various elementary steps are discussed, and the values that their relative rates must assume for successful Fischer–Tropsch chain growth are outlined. Within the Sachtler–Biloen kinetics scheme, a high chain-growth probability is obtained when chain termination is rate limiting. Consequently, CO dissociation has to be facile. The “C1” species that is incorporated into the growing chain appears to be “CH” or “CH2”; thus, these species must be present in high surface concentrations. Brønsted–Evans–Polanyi relationships are used to link activation energies to surface reactivity. The structure sensitivity of the elementary reaction steps, specifically, initiation, chain growth, and termination, is analyzed. On the basis of these considerations, one can understand why particular metals are suitable Fischer–Tropsch catalysts.
Abstract: 2011 Publication year: 2011 Source:Advances in Catalysis, Volume 54
Vanadium phosphates have been established as selective hydrocarbon oxidation catalysts for more than 40 years. Their primary use commercially has been in the production of maleic anhydride (MA) from n-butane. During this period, improvements in the yield of MA have been sought. Strategies to achieve these improvements have included the addition of secondary metal ions to the catalyst, optimization of the catalyst precursor formation, and intensification of the selective oxidation process through improved reactor technology. The mechanism of the reaction continues to be an active subject of research, and the role of the bulk catalyst structure and an amorphous surface layer are considered here with respect to the various V–P–O phases present. The active site of the catalyst is considered to consist of V4+ and V5+ couples, and their respective incidence and roles are examined in detail here. The complex and extensive nature of the oxidation, which for butane oxidation to MA is a 14-electron transfer process, is of broad importance, particularly in view of the applications of vanadium phosphate catalysts to other processes. A perspective on the future use of vanadium phosphate catalysts is included in this review.
Abstract: 2011 Publication year: 2011 Source:Advances in Catalysis, Volume 54
Structured catalysts and reactors offer high precision in catalysis at all relevant scales of the catalytic process, from that of the catalytic species up to that of the reactor. Monoliths are the prime example of such catalysts because of their wide practical applications. Thus, monoliths are emphasized in this review, but most of the text is also relevant to all structured reactors, including microreactors. Conceptually, monoliths exhibit more degrees of freedom in design than conventional reactors, such as fixed-bed and slurry reactors. The flow in monoliths is laminar, and as a consequence, they are associated with high efficiency and minimum chaotic characteristics. The hydrodynamics of single-phase and multiphase flow reactors are remarkably simple. Under most conditions in multiphase systems, Taylor flow (segmented flow) prevails, associated with high rates of mass transfer notwithstanding low energy consumption, but under other conditions, the film flow regime can be realized either in cocurrent or in countercurrent flow of gas and liquid streams, making the monolith a good structure for novel technologies such as catalytic distillation. Monoliths offer freedom in the design of reactor configuration. Examples are loop reactors for strong exo- and endothermic reactions, which allow a combination with separate heat exchange without the penalty of a large energy consumption, which otherwise is usually unavoidable for the large recycle ratios needed. For applications in fine chemistry and in the laboratory, a convenient monolithic stirred reactor is presented. The principal bottleneck for practical application of monolith reactors is the synthesis rather than the design of the catalytic monolith. When a monolith reactor is considered as an alternative to a fixed-bed reactor packed with commercially available catalyst particles, the grim reality is that a development program is needed to producing the catalytic monolith. Therefore, preparation methods including synthesis of various coating layers and the deposition of active catalytic species are described in detail here. This chapter also includes an exhaustive review of practical applications of monolith reactors. In applications in which high gas flow rates have to be accommodated, monoliths monoliths are the state of the art in many cases, exemplified by automobile exhaust abatement reactors—because of the popularity of automobiles, more monolithic reactors are being used than fixed-bed reactors. Applications in processes with liquid-phase and gas–liquid-phase reactants are scarce, but one well-known commercial process (the reduction step in the production of hydrogen peroxide) shows the feasibility of monoliths. Several processes are in the development stage. Included in the review are an assessment of the impact of these reactors on process intensification and applications in biotechnology and photocatalysis.
Subscription journal
[3043 journals]
