Supported catalysts cation

There is a wide variety of solid electrolytes and, depending on their composition, these anionic, cationic or mixed conducting materials exhibit substantial ionic conductivity at temperatures between 25 and 1000°C. Within this very broad temperature range, which covers practically all heterogeneous catalytic reactions, solid electrolytes can be used to induce the NEMCA effect and thus activate heterogeneous catalytic reactions. As will become apparent throughout this book they behave, under the influence of the applied potential, as active catalyst supports by becoming reversible in situ promoter donors or poison acceptors for the catalytically active metal surface. 

Fig. 9 Dependence of catalytic activity of MgO-supported catalysts containing cationic gold and (except in the most active catalyst) gold clusters for ethene hydrogenation at 760 Torr and 353 K (reactive mixture of He, ethene, and H2—ethene partial pressure, r ethene. 40 Torr Phydrogen. 160 Torr the balance He). Note the nonlinearity of the scale at the top [53]...

The present model deals with a supported transition metal cation which is highly dispersed, at the molecular scale, on an oxide, or exchanged in a zeolite. In the case of zeolite-supported cations, the formation of different metal species in metal/zeolite catalysts (metal oxides, metal oxocations, besides cationic species) has been considered by different authors who have suggested these species to play key roles in SCR catalysis [14,15], This supported cation can also be considered as located at a metal oxide/support interface. 

As can be seen, the catalytic process over a zeolite-supported cation, or an oxide-supported cation, can be considered as a supported homogeneous catalysis, as far as adsorbed reactants and products behave like reactive ligands. The model developed for lean DcNO. catalysts over supported cations (function 3), as well as this supported homogeneous catalysis approach, is also suitable for stoichiometric mixture (TWC) comprising CO and H2 as reductants over supported transition metal cations [20-22],... 

The dispersion and solid-state ion exchange of ZnCl2 on to the surface of NaY zeolite by use of microwave irradiation [17] and modification of the surface of active carbon as catalyst support by means of microwave induced treatment have also been reported [18]. The ion-exchange reactions of both cationic (montmorillonites) and anionic clays (layered double hydroxides) were greatly accelerated under conditions of microwave heating compared with other techniques currently available [19.]... 

Electron spin resonance (ESR) signals, detected from phosphinated polystyrene-supported cationic rhodium catalysts both before and after use (for olefinic and ketonic substrates), have been attributed to the presence of rhodium(II) species (348). The extent of catalysis by such species generally is uncertain, although the activity of one system involving RhCls /phosphinated polystyrene has been attributed to rho-dium(II) (349). Rhodium(II) phosphine complexes have been stabilized by steric effects (350), which could pertain to the polymer alternatively (351), disproportionation of rhodium(I) could lead to rhodium(II) [Eq. (61)]. The accompanying isolated metal atoms in this case offer a potential source of ESR signals as well as the catalysis. 

Characterization techniques continue to develop and will impact their application to zeolitic systems. Aberration corrected electron microscopes are now being used to improve our understanding of catalysts and other nano-materials and will do the same for zeolites. For example, individual Pt atoms dispersed on a catalyst support are now able to be imaged in the STEM mode [252]. The application of this technique for imaging the location of rare-earth or other high atomic number cations in a zeolite would be expected to follow. Combining this with tomography... 

Organic molecules spontaneously form corresponding cation-radicals on inclusion within activated zeolites (Yoon and Kochi 1988, Yoon 1993, Pitchumani et al. 1997). Zeolites are crystalline alu-mosilicate minerals that are widely used as sorbents, ion exchangers, catalysts, and catalyst supports. As zeolites act as electron acceptors due to the presence of Lewis- or Broensted-acid sites, confined organic compounds occur to be electron donors. Frequently, the interaction of electron donor with electron acceptor centers spontaneously generates cation-radicals and traps the ejected electrons. 

Theoretical studies on the Beckmann rearrangement mechanism over zeolite catalyst supported by experimental data have increased. The catalytic activity of the zeohte is determined by Brpnsted and Lewis acid sites created by protonation or activation by metallic cations. The reactivity of the acid sites is strongly influenced by the geometry and flexibility of the zeolite framework ". ... 

The development of mesoporous materials with more or less ordered and different connected pore systems has opened new access to large pore high surface area zeotype molecular sieves. These silicate materials could be attractive catalysts and catalyst supports provided that they are stable and can be modified with catalytic active sites [1]. The incorporation of aluminum into framework sites of the walls is necessary for the establishment of Bronsted acidity [2] which is an essential precondition for a variety of catalytic hydrocarbon reactions [3], Furthermore, ion exchange positions allow anchoring of cationic transition metal complexes and catalyst precursors which are attractive redox catalytic systems for fine chemicals [4]. The subject of this paper is the examination of the influence of calcination procedures, of soft hydrothermal treatment and of the Al content on the stability of the framework aluminum in substituted MCM-41. The impact on the Bronsted acidity is studied. 

This evidence supports the concept that the Ziegler polymerization of styrene is by catalysts with cationicities which lie between the cationic Friedel-Crafts system and the anionic alkyl sodium system. Its character can be shifted depending on the ratio of the aluminum to titanium. 

The use of hydroxyapatites as a catalyst support has the following advantages (1) well-defined monomeric active species can be immobilized on the surface based on multiple functionalities, for example, cation exchange ability, adsorption capacity and nonstoichiometry (2) their hydrophilic character allows smooth reactions under aqueous conditions and (3) due to their robust structure, no leaching of metals occurs. 

A Ni bifunctional catalyst supported in a homoionic natural clinoptilolite will be used, as an example, to further explain the methodology of preparation of this type of catalysts [18]. As was previously commented, the thermal reduction of zeolites previously exchanged with metals is the method currently used for the preparation of bifunctional catalysts for hydrocarbon conversion. To produce these catalysts, synthetic [19,20] and natural zeolites [18,21-23] are used. During this procedure, the zeolite is exchanged with the cationic form of the metal that will be used as the catalyst and afterward the obtained exchanged zeolite is reduced in a H2 atmosphere at about 450°C and maintained at this temperature for about 2h [18,19-23],... 

As fax as we know, only the bis-ethylenediamine (or 1,2-diaminoethane) Aum cation, [Au(en)2]3+, has been used to prepare gold catalysts by cation exchange of zeolites, or cation adsorption on oxide supports synthesis of the complex with chloride counter-ions is easy.98... 

Figure 10.4 Compensation plot for various supported gold catalysts the cation of the support is shown. The filled point is for a Cu/ZnO-A Os low-temperature shift catalyst the points for Ti02-supported catalysts on the upper line were made by deposition-participation all those on the lower line were made by coprecipitation. See Table 10.2 for further details.

However, equation (3) still contains two unknowns the work function of the metal and the work function of the gold deposit. A multilaboratory study has shown that neither carbon nor gold provide a suitable internal standard for catalyst supports (34). Alternatively, the binding energy scale has been referenced to a core level of the support metal cation, for example, the Si 2p peak of silica. This is no improvement. The work function of a high surface area, amorphous catalyst support has never been measured. 

The rhodium-catalyzed hydroformylation of 1-hexene using a polar-phase solvent system (30% water by volume in acetone) has resulted in improvements in rate and chemoselectivity for catalysts supported by the tetraphosphine ligand et,ph-P4. A cationic rhodium dimer comprising... 

Over the past 15-20 years, there has been a renewed and growing interest in the use of clay minerals as catalysts or catalyst supports. Most of this interest has focused on the pillaring of smectite clays, such as montmorillonite, with various types of cations, such as hydrated metal cations, alkylammonium cations and polycations, and polynuclear hydroxy metal cations (1-17). By changing the size of the cation used to separate the anionic sheets in the clay structure, molecular sieve-like materials can be made with pore sizes much larger than those of conventional zeolites. 

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