Transition-metal heterogeneous catalysi

Medford AJ, et al. From the Sabatier principle to a predictive theory of transition-metal heterogeneous catalysis. J Catal 2015 328 36-42. 

The rediscovery of lanthanides, about 190 years after their first appearance, in the catalysis field now stimulates the study and the interest in these elements at a high level for many applications. In the absence of serious problems coming from purity, availability, toxicity, and cost, the performance of lanthanides appears in many cases favourable with respect to that of the more conventional d-transition metals. Heterogeneous Ln-containing catalysts show unique behaviour in hydrocarbon cracking and are now proposed for many other industrial processes. Homogeneous catalysts based on lanthanides, as competitors of other already applied transition elements. 

The product D is produced by the transition-metal homogeneous catalysis in at least one catalytic cycle. Contributions to the rate of formation of D may also arise from stoichiometric reactions or heterogeneous catalytic reactions on suspended colloidal metal, suspended metal particles, or metal deposited on the walls of the vessel, etc. The total rate of reaction is noted (mol/s). Since the system is time dependent, and in particular due to the need to transform the catalyst precursor to intermediates, the maximum rate of product formation Pd occurs at t > to-... 

ILs are widely used in transition metal chemistry, such as biphasic catalytic system in 7i-acceptor ligand [41], Several reviews have been published in which ILs occupied a central theme due to their use in homogeneous and heterogeneous catalyses as well as for transition metal-mediated catalysis and organometallic reactions [42]. IL is used as a solvent in organic and bioorganic reactions [43, 44] it also acts as an organocatalyst [45]. 

In recent years, much attention has been focused on electrochemical studies of metalloporphyrins, not only as mimetic compounds of the iron porphyrin unit in heme proteins but also as potential electrocatalysts . Metalloporphyrins have been found to be applicable in both homogeneous and heterogeneous catalysis - and, because oxygen can be reduced directly through a 4-electron pathway on some transition metal porphyrins, catalysis in the heterogeneous electrochemical oxygen reduction reaction has received particular attention The application of metalloporphyrins to heterogeneous electrocatalysis requires their attachment to solid electrodes which can be realized based on chemisorption, chemical reactions with previously functionalized electrodes, chemical reactions with a functionalized polymer, incorporation of the porphyrin with the polymer film and electrochemical polymerization. 

The composition and chemical state of the surface atoms or molecules are very important, especially in the field of heterogeneous catalysis, where mixed-surface compositions are common. This aspect is discussed in more detail in Chapter XVIII (but again see Refs. 55, 56). Since transition metals are widely used in catalysis, the determination of the valence state of surface atoms is important, such as by ESCA, EXAFS, or XPS (see Chapter VIII and note Refs. 59, 60). 

The microscopic understanding of tire chemical reactivity of surfaces is of fundamental interest in chemical physics and important for heterogeneous catalysis. Cluster science provides a new approach for tire study of tire microscopic mechanisms of surface chemical reactivity [48]. Surfaces of small clusters possess a very rich variation of chemisoriDtion sites and are ideal models for bulk surfaces. Chemical reactivity of many transition-metal clusters has been investigated [49]. Transition-metal clusters are produced using laser vaporization, and tire chemical reactivity studies are carried out typically in a flow tube reactor in which tire clusters interact witli a reactant gas at a given temperature and pressure for a fixed period of time. Reaction products are measured at various pressures or temperatures and reaction rates are derived. It has been found tliat tire reactivity of small transition-metal clusters witli simple molecules such as H2 and NH can vary dramatically witli cluster size and stmcture [48, 49, M and 52]. 

This type of co-catalytic influence is well loiown in heterogeneous catalysis, in which for some reactions an acidic support will activate a metal catalyst more efficiently than a neutral support. In this respect, the acidic ionic liquid can be considered as a liquid acidic support for the transition metal catalysts dissolved in it. 

However, research into transition metal catalysis in ionic liquids should not focus only on the question of how to make some specific products more economical or ecological by use of a new solvent and, presumably, a new multiphasic process. Since it bridges the gap between homogeneous and heterogeneous catalysis, in a novel and highly attractive manner, the application of ionic liquids in transition metal catalysis gives access to some much more fundamental and conceptual questions for basic research. 

In comparison with traditional biphasic catalysis using water, fluorous phases, or polar organic solvents, transition metal catalysis in ionic liquids represents a new and advanced way to combine the specific advantages of homogeneous and heterogeneous catalysis. In many applications, the use of a defined transition metal complex immobilized on a ionic liquid support has already shown its unique potential. Many more successful examples - mainly in fine chemical synthesis - can be expected in the future as our loiowledge of ionic liquids and their interactions with transition metal complexes increases. 

The past fifteen years have seen evidence of great interest in homogeneous catalysis, particularly by transition metal complexes in solution predictions were made that many heterogeneous processes would be replaced by more efficient homogeneous ones. There are two motives in these changes—first, intellectual curiosity and the belief that we can define the active center with... 

Research into cluster catalysis has been driven by both intrinsic interest and utilitarian potential. Catalysis involving "very mixed -metal clusters is of particular interest as many established heterogeneously catalyzed processes couple mid and late transition metals (e.g., hydrodesulfurization and petroleum reforming). Attempts to model catalytic transformations arc summarized in Section II.F.I., while the use of "very mixed -metal clusters as homogeneous and heterogeneous catalysis precursors are discussed in Sections I1.F.2. and I1.F.3., respectively. The general area of mixed-metal cluster catalysis has been summarized in excellent reviews by Braunstein and Rose while the tabulated results are intended to be comprehensive in scope, the discussion below focuses on the more recent results. 

Heterogeneous catalysis by metals has been of long-standing interest, with bimetallic catalysts a particular focus.Transition metal carbonyls have... 

In the sixties of past century, a few patents issued to Bergbau Chemie [5,48,49] and to Mobil Oil [50-52], respectively described the use of CFPs as supports for catalytically active metal nanoclusters and as carriers for heterogenized metal complexes of catalytic relevance. For the latter catalysts the term hybrid phase catalysts later came into use [53,54], At that time coordination chemistry and organo-transition metal chemistry were in full development. Homogeneous transition metal catalysis was expected to grow in industrial relevance [54], but catalyst separation was generally a major problem for continuous processing. That is why the concept of hybrid catalysis became very popular in a short time [55]. 

Transition metal NPs dispersed in ILs are recognized as suitable catalyst systems for many reaction types with both typical homogeneous and heterogeneous catalysis (see Sections 1.3.1-1.3.5). The most investigated reactions are the hydrogenation of multiple bonds and arenes [1, 5, 12, 13, 43, 44, 54, 80, 89, 92], carbon-carbon cross-... 

An unusual ee-screening system for enantioselective transition metal catalysts is based on IR-thermo-graphy,55 which had previously been used in heterogeneous catalysis.36,81,82 Using an AIM-2562 IR... 

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