There are two main disciplines in catalysis research -- homogeneous and heterogeneous catalysis. This is due to the fact that the catalyst is either in the same phase (homogeneous catalysis) as the reaction being catalyzed or in a different phase (heterogeneous catalysis). Over the past decade, various approaches have been implemented to combine the advantages of homogeneous catalysis (efficiency, selectivity) with those of heterogeneous catalysis (stability, recovery) by the heterogenization of homogeneous catalysts or by carrying out homogeneous reactions under heterogeneous conditions. 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. As such, it highlights structural analogies and shows mechanistic parallels between the two, while additionally presenting kinetic analysis methods and models that either work for both homogeneous and heterogeneous catalysis. Chapters cover asymmetric, emulsion, phase-transfer, supported homogeneous, and organocatalysis, as well as in nanoreactors and for specific applications, catalytic reactions in ionic liquids, fluorous and supercritical solvents and in water. Finally, the text includes computational methods for investigating structure-reactivity relations. With its wealth of information, this invaluable reference provides academic and industrial chemists with novel concepts for innovative catalysis research.

This interconversion occurs via complex multistep, multielectron reactions, which can be carried out by either metallic heterogeneous or molecular homogeneous electrocatalysts. Metallic heterogeneous catalysts have a continuum of electronic states that distribute the redox burden of multielectron reactions, allowing for efficient catalysis. However, heterogeneous catalysts display a variety of active sites and local electronic structures, and are difficult to fine-tune at a molecular level. On the other hand, homogeneous catalysts allow a great degree of synthetic control over the catalytic active site. Moreover, the relative ease in spectroscopic characterization allows a mechanistic understanding of molecular catalysis at a level that is unattainable for heterogeneous catalysis. To bridge the advantages of both types of catalysts, we have developed a surface functionalization strategy for conjugating molecularly well-defined active sites to graphitic carbon surfaces. First, I will discuss the preparation and characterization of two new types of conjugating N-heterocyclic linkages to graphitic carbon surfaces. This work presents a general method for characterizing modified carbon surfaces with molecular-level structural detail. Then, I will present the electrocatalytic carbon dioxide reduction activity of a graphite-conjugated rhenium catalyst, and compare its catalytic behavior to that of a molecular analog. Electrochemical and spectroscopic data show that graphite-conjugated catalysts do not behave identically to their molecular analogs, but rather show properties similar to that of metallic heterogeneous catalysts, providing a unique bridge between the worlds of heterogeneous and homogeneous catalysis. Finally, in the appendix, I will present a chapter on the stability of graphite-conjugated linkages under electrochemical polarization, followed by a chapter on catalyzing the reduction of molecular pyridinium species using a graphite-conjugated rhodium catalyst.

Catalysts, heterogeneous, homogeneous, and enzymatic, are comprised of nanometer-sized inorganic and/or organic components. They share molecular factors including charge, coordination, interatomic distance, bonding, and orientation of catalytically active atoms. By controlling the governing catalytic components and molecular factors, catalytic processes of a multichannel and multiproduct nature could be run in all three catalytic platforms to create unique end-products. Unifying the fields of catalysis is the key to achieving the goal of 100% selectivity in catalysis. Recyclable catalysts, especially those that display selective reactivity, are vital for the development of sustainable chemical processes. Among available catalyst platforms, heterogeneous catalysts are particularly well-disposed toward separation from the reaction mixture via filtration methods, which renders them readily recyclable. Furthermore, heterogeneous catalysts offer numerous handles - some without homogeneous analogues - for performance and selectivity optimization. These handles include nanoparticle size, pore profile of porous supports, surface ligands and interface with oxide supports, and flow rate through a solid catalyst bed. Despite these available handles, however, conventional heterogeneous catalysts are themselves often structurally heterogeneous compared to homogeneous catalysts, which complicates efforts to optimize and expand the scope of their reactivity and selectivity. Ongoing efforts are aimed to address the above challenge by heterogenizing homogeneous catalysts, which can be defined as the modification of homogeneous catalysts to render them in a separable (solid) phase from the starting materials and products. Specifically, we grow the small nanoclusters in dendrimers, a class of uniform polymers with the connectivity of fractal trees and generally radial symmetry. Thanks to their dense multivalency, shape persistence and structural uniformity, dendrimers have proven to 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 powerful platform for nanoparticle catalysis, our studies suggest that in some cases interband transitions should be considered as an alternative mechanism of light-driven nanoparticle catalysis. The benefits already demonstrated by plasmonic nanostructures as catalysts provided the impetus for examining complementary activation modes based on the metal nanoparticle itself. Leveraging these transitions has the potential to provide a means to highly active catalysis modes that would otherwise be challenging to access. For example, for the preparation of highly active metal catalysts on a subnanosized scale is challenging, thus limiting their exploitation and study in catalysis. Our work suggests a novel and facile strategy for the formation of highly active gold nanocluster catalysts by light illumination of the interband transitions in the presence of the appropriate substrate.

Homogeneous and Heterogeneous Catalysis

Contains a balanced discussion of homogeneous catalytic reactions that are used in industry, featuring every documented example employed in a current commercial process, or that have a broad application in the organic synthesis laboratory. Incorporates synthesis with chiral catalysts in chapters on hydrogenation, CO chemistry and olefin oxidation. New additions include Tennessee Eastman's coal-based acetic anhydride plant and IFP's Dimersol process for dimerizing propylene as well as major changes in the areas on pharmaceuticals, flavors, fragrances, agricultural and electronic chemicals.

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 catalysis Basis for understanding and designing experiments in the field Allows reader to understand catalyst design principles Introduction to important elements of energy transformation technology Test driven at Stanford University over several semesters

The field of transition metal catalysis has experienced incredible growth during the past decade. The reasons for this are obvious when one considers the world's energy problems and the need for new and less energy demanding syntheses of important chemicals. Heterogeneous catalysis has played a major industrial role; however, such reactions are generally not selective and are exceedingly difficult to study. Homogeneous catalysis suffers from on-site engineering difficulties; however, such reactions usually provide the desired selectivity. For example, Monsanto's synthesis of optically-active amino acids employs a chiral homogeneous rhodium diphosphine catalyst. Industrial uses of homogeneous catalyst systems are increasing. It is not by accident that many homogeneous catalysts contain tertiary phosphine ligands. These ligands possess the correct steric and electronic properties that are necessary for catalytic reactivity and selectivity. This point will be emphasized throughout the book. Thus the stage is set for a comprehensive be treatment of the many ways in which phosphine catalyst systems can designed, synthesized, and studied.

This book concentrates on industrially relevant reactions which are catalyzed by heterogeneous and homogeneous catalysts. Homogeneous catalysis by metal complexes is treated jointly with heterogeneous catalysis using metallic and non-metallic solids. In both areas the high degree of sophistication of spectroscopic techniques and theoretical modelling has led to an enormous increase in our understanding at the molecular level. This holds for the kinetics of the reactions and the reactivities of the catalysts, as well as for the syntheses of the catalytic materials. The development of catalysis science since the first edition of this book has necessitated a thorough revision, including special chapters on biocatalysis, catalyst characterization and adsorption methods. The multidisciplinary nature of catalysis is reflected in the choice of a novel combination of basic disciplines which will be refreshing and inspiring to readers.

Catalysts are now widely used in both laboratory and industrial-scale chemistry. Indeed, it is hard to find any complex synthesis or industrial process that does not, at some stage, utilize a catalytic reaction. The development of homogeneous transition metal catalysts on the laboratory scale has demonstrated that these systems can be far superior to the equivalent heterogeneous systems, at least in terms of selectivity. is an increasing interest in this field of research from both an Thus, there academic and industrial point of view. In connection with the rapid developments in this area, four universities from the E.E.C (Aachen, FRG; Liege, Belgium; Milan, Italy; and Lille, France) have collaborated to organise a series of seminars for high-level students and researchers. These meetings have been sponsored by the Commission of the E.E.C and state organizations. The most recent of these meetings was held in Lille in September 1985 and this book contains updated and expanded presentations of most of the lectures given there. These lectures are concerned with the field of homogeneous transition metal catalysis and its application to the synthesis of organic intermediates and fine chemicals from an academic and industrial viewpoint. The continuing petroleum crisis which began in the early 1970s has given rise to the need to develop new feedstocks for the chemical industry.

This book presents the latest research in the field of heterogeneous catalysis. Heterogeneous catalysis and homogeneous catalysis are important factors in increasing the development of green chemistry. Some of the challenges that we are responsible for are directing research efforts toward increasing the kinetics of heterogeneous catalysis to homogeneous catalysis levels, improving the recyclability of the catalysts, and developing new supports that can act as catalysts or cocatalysts. Following reaction kinetics and mechanisms on supported catalysts provides the degree of precision and accuracy already enjoyed by the homogeneous catalysis community. The editors present an easily-accessible digest for researchers and a reference aimed at offering guidance to new researchers in the field. Priced at £110.00 or US$180.00.