Zeolites metal oxide cluster

Side-Chain Alkylation. There is continued interest in the alkylation of toluene with methanol because of the potential of the process in practical application to produce styrene.430 Basic catalysts, specifically, alkali cation-exchanged zeolites, were tested in the transformation. The alkali cation acts as weak Lewis acid site, and the basic sites are the framework oxygen atoms. The base strength and catalytic activity of these materials can be significantly increased by incorporating alkali metal or alkali metal oxide clusters in the zeolite supercages. Results up to 1995 are summarized in a review.430... 

Alkenes may also be used as reagents in side-chain alkylation. Zeolites with occluded alkali metal and alkali metal oxide clusters were tested in alkylation of toluene with ethylene439 440 Alkali metal clusters created by decomposing Na or... 

Ichikawa M, Pan W, Imada Y, Yamaguchi M, Isobe K, Shido T (1996) Surface-grafted metal oxide clusters and metal carbonyl clusters in zeolite micropores XAES/ETIR/TPD characterization and catalytic behavior. J Mol Catal A Chem 107 23... 

The catalytic activity of alkali metal oxide clusters encapsulated in the zeolitic cages of faujasite has been tested in different reactions catalyzed by basic sites, e. g. olefin isomerization [75,77], isopropanol decomposition [67,68], and Knoe-venagel condensation [73,74,78]. 

The formation of oxide-hydroxide metal clusters is considered in Sect. 20.4. Various places of their localization are discussed. One of them is associated with accommodation of metal oxide species in the cationic position of zeolites. The (Zn302) cluster formation was smdied and its activity in the dehydrogenation of ethane was calculated. Besides the condensation of polynuclear oxide species in ion-exchange positions a possibility of the grafting of small metal oxide clusters to zeolite or to pure silica lattice was considered on the example of immobilization of ZnO, (ZnO)2 and (ZnO)3 species. 

Figure A12. A schematic picture of the process of embedding for benzene adsorption at a metal oxide cluster fixed into the pore of a zeolite. The inner region which defines the adsorption site can be treated with a higher level of theory whereas the outer region is defined with a significantly lower level of theory such as force field. An overlap or link region is defined between the two in order to transfer information effectively between the two models.

Oxygen atoms in a zeolite lattice have an intrinsic Lewis base character due to the electron pairs they can donate and to the partial negative charges they bear. Silicon or aluminum atoms provide partial positive charges, which reduce the strength of such a donation [8,54]. However, every zeolite framework possesses an intrinsic Lewis base character. Additional basic sites can be created by metal or metal oxide clusters within the micropores of the zeolite [54]. The different basic sites will be discussed in the following paragraphs. 

Impregnation followed by thermal treatment is commonly used to prepare alkali metal oxide or alkaline earth metal oxide clusters in molecular sieves in order to obtain catalysts with basic properties. A first hint at the usefulness of such procedures was published in 1984 Lacroix et al. reported that cesium-exchanged zeolite X is more active in the side-chain alkylation of toluene with methanol when left unwashed after the cation exchange [1]. Hathaway and Davis [2-4] carried out further systematic studies on the preparation of intrazeoUtic oxide clusters with basic properties. These authors described two methods for the introduction of alkali metal oxides into the pores of faujasites [2j When zeolites X and Y, ion-exchanged at room temperature with aqueous solutions of alkali metal acetates or... 

Abstract This review is a summary of supported metal clusters with nearly molecular properties. These clusters are formed hy adsorption or sirnface-mediated synthesis of metal carbonyl clusters, some of which may he decarhonylated with the metal frame essentially intact. The decarhonylated clusters are bonded to oxide or zeolite supports by metal-oxygen bonds, typically with distances of 2.1-2.2 A they are typically not free of ligands other than the support, and on oxide surfaces they are preferentially bonded at defect sites. The catalytic activities of supported metal clusters incorporating only a few atoms are distinct from those of larger particles that may approximate bulk metals. 

Supported metal carbonyl clusters are alternatively formed from mononuclear metal complexes by surface-mediated synthesis [5,13] examples are [HIr4(CO)ii] formed from Ir(CO)2(acac) on MgO and Rh CCOlie formed from Rh(CO)2(acac) on y-Al203 [5,12,13]. These syntheses are carried out in the presence of gas-phase CO and in the absence of solvents. Synthesis of metal carbonyl clusters on oxide supports apparently often involves hydroxyl groups or water on the support surface analogous chemistry occurs in solution [ 14]. A synthesis from a mononuclear metal complex precursor is usually characterized by a yield less than that attained as a result of simple adsorption of a preformed metal cluster, and consequently the latter precursors are preferred when the goal is a high yield of the cluster on the support an exception is made when the clusters do not fit into the pores of the support (e.g., a zeolite), and a smaller precursor is needed. 

Fierro-Gonzalez, J.C., Kuba, S., Hao, Y. et al. (2006) Oxide- and zeolite-supported molecular metal complexes and clusters physical characterization and determination of structure, bonding, and metal oxidation state, J. Phys. Chem. B, 110, 13326. 

The induction of steric effects by the pore walls was first demonstrated with heterogeneous catalysts, prepared from metal carbonyl clusters such as Rh6(CO)16, Ru3(CO)12, or Ir4(CO)12, which were synthesized in situ after a cation exchange process under CO in the large pores of zeolites such as HY, NaY, or 13X.25,26 The zeolite-entrapped carbonyl clusters are stable towards oxidation-reduction cycles this is in sharp contrast to the behavior of the same clusters supported on non-porous inorganic oxides. At high temperatures these metal carbonyl clusters aggregate to small metal particles, whose size is restricted by the dimensions of the zeolitic framework. Moreover, for a number of reactions, the size of the pores controls the size of the products formed thus a higher selectivity to the lower hydrocarbons has been reported for the Fischer Tropsch reaction. 

Li and Armor reported that Co-exchanged zeolites present a very high catalytic performance for the CH4-SCR, even in oxygen excess conditions [1, 3], Bimetallic Pt-and Pd-Co zeolites have revealed an increase of activity, selectivity towards N2 and stability, when compared with monometallic Co catalysts [4-8] even in the presence of water in the feed. Recent works show that these catalytic improvements are due to the presence of specific metal species as isolated metal ions, clusters and oxides and their location inside the cavities or in the external surface of zeolite crystallites [9, 10],... 

Full catalyst formulations consist of zeolite, metal and a binder, which provides a matrix to contain the metal and zeolite, as well as allowing the composite to be shaped and have strength for handling. The catalyst particle shape, size and porosity can impact the diffusion properties. These can be important in facile reactions such as xylene isomerization, where diffusion of reactants and products may become rate-limiting. The binder properties and chemistry are also key features, as the binder may supply sites for metal clusters and affect coke formation during the process. The binders often used for these catalysts include alumina, silica and mixtures of other refractory oxides. 

A comparable paradigm of success is still to be established for more complex catalytic materials e.g., finite metal/compound clusters, mixed oxides, zeolites), many of which are highly important technological catalysts and often contain multiple active centers that are required to achieve a series of specific transformations. The local structures of these catalysts and... 

Approaches to the formation of three new types of micro-porous materials that complement zeolites will be discussed. In each case, whether metal coordination polymers, metal-linked ceramic oxide clusters, or new hybrids containing both coordination and ceramic components, engineering of the Secondary Building Unit (SBU) is of critical importance. Successful examples of these approaches include the first thermally stable 3-D micro-porous coordination polymer with chemical functionalizability [Cu3(TMA)2(H20)3] , as well as a 3-D micro-porous cluster based material [V,2B18O60H8(Cd(en)(H2O) 3]". ... 

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