Transition metal cations, catalysts

Lewis acids are defined as molecules that act as electron-pair acceptors. The proton is an important special case, but many other species can play an important role in the catalysis of organic reactions. The most important in organic reactions are metal cations and covalent compounds of metals. Metal cations that play prominent roles as catalysts include the alkali-metal monocations Li+, Na+, K+, Cs+, and Rb+, divalent ions such as Mg +, Ca +, and Zn, marry of the transition-metal cations, and certain lanthanides. The most commonly employed of the covalent compounds include boron trifluoride, aluminum chloride, titanium tetrachloride, and tin tetrachloride. Various other derivatives of boron, aluminum, and titanium also are employed as Lewis acid catalysts. 

Other authors also determined by FTIR that organic nitrocompounds are formed as primary products of the NO CH4-SCR reaction on ZSM-5-based catalysts [121-124], They preadsorbed nitromethane on the sample placed in the IR cell and followed by IR its transformation into other intermediates under 02 and NO versus time at different temperatures. For Cu- and Co-ZSM-5, it was shown that around 300°C adsorbed nitromethane is easily converted into isocyanates and then melamine via polymerization of the former species. Both species easily interact with molecular oxygen, while no reaction with NO is observed and the reactivity depends on the temperature and the nature of the transition metal cation. 

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],... 

Acidic clay catalysts can also be used in alkylation with alcohols 98 The main advantages of these catalysts are the reduced amount necessary to carry out alkylation compared with conventional Friedel-Crafts halides, possible regeneration, and good yields. Natural montmorillonite (K10 clay) doped with transition metal cations was shown to be an effective catalyst 200... 

Mechanisms Symptoms Carbon corrosion (air-air start) Gas impurities (e.g., CO, H2S, Sp2, ) Contaminants (e.g. some transition metal cations, anions) Catalyst instability (pt sintering, dissolution, re-crystallization) GDL loss of wet-proof (flooding) Seal failure (gross leaking) Membrane failure (pinholing, and tear)... 

Very striking results on the interactions of molecules with a catalyst have been recently reported in zeolite catalysis because of the well ordered structure of these materials it is worth mentioning the subjects of zeolite design [10] and of acidic properties of metallosilicates [11]. In other areas where polycrystallinic or even amorphous materials arc applied, highly interesting results are now numerously emerging (such as hydrocarbon oxidation on vanadium-based catalysts [12] location of transition metal cations on Si(100) [13] CO molecules on MgO surfaces [14] CH4 and O2 interaction with sodium- and zinc-doped CaO surfaces [15] CO and NO on heavy metal surfaces [16]). An illustration of the computerized visualization of molecular dynamics of Pd clusters on MgO(lOO) and on a three-dimensional trajectory of Ar in Na mordenitc, is the recent publication of Miura et al. [17]. 

Unlike early transition metal polymerization catalysts which do not tolerate functional groups, cationic palladium complexes are able to copolymerize ethylene with methyl acrylate.128... 

Cation exchanged zeolites are successfully applied as catalysts or selective sorbents in separation technologies. " For both catalytic and sorption processes a concerted action of polarizing cations and basic oxygen atoms is important. In addition, transition metal cation embedded in zeolites exhibit peculiar redox properties because of the lower coordination in zeolite cavities compared to other supports." " Therefore, it is important to establish the strength and properties of active centers and their positions in the zeolite structure. Various experimental methods and simulation techniques have been applied to study the positions of cations in the zeolite framework and the interaction of the cations with guest molecules.Here, some of the most recent theoretical studies of cation exchanged zeolites are summarized. 

Use of Catalysts Containing Transition Metal Cations. Ethyl -ene being alkylated over certain zeolite catalysts reacts specifically. Ethylene can not, however, be alkylated with Isobutane In the presence of H2SO., because of the formation of stable ethylsulphates. We examined the Isobutane - ethylene alkylation over crystalline aluminosilicates and found that those catalysts containing RE and/or Ca In combination with transition metal cations were most active. The alkylation has resulted In not hexanes as would be expected, but an alkylate containing octane Isomers as the major product (about 80%). Moreover, the product composition was similar to that obtained from n-butene over CaREY. The TMP-to-DMH ratios were 7.8 and 7.1 respectively. 

Dimerization presumably takes place on the transition metal-containing sites, and alkylation on the acidic sites of zeolltic surface. The sodium form of zeolite exchanged with transition metal cations Is capable of dimerization (and further polymerization), but does not practically exhibit alkylating capacity. This explains the composition of the product obtained from ethylene and Isobutane over this catalyst (Table V, column 3). 

Ca cation Introduction leads to the catalyst containing both kinds of catalytic sites, and the ethylene-isobutane Interaction over this catalyst proceeds through dimerization to the alkylation step, yielding high quality alkylate (Table V, column 4). The alkylate yield was 120X. The reaction does not occur unless transition metal cations are present In the catalyst even though the latter may contain acidic sites (CaY for example). It Is understood that no butenes are formed In this case, and ethylene does not Interact directly with Isobutane under the conditions of this experiment. 

Temperature-programmed reduction and desorption (TPR, TPD) have been applied to study the stability of Pt-Co bimetallic particles entrapped in NaY zeolite cages upon O2 oxidation and reaction with surface protons generated during the reduction of transition metal cations. Oxidation of Pt/NaY catalyst with O2 at 573 K causes shift of TPR peak to lower temperature due to formation of partially oxidized Pt particles. Similar treatment for Pt-Co/NaY bimetallic catalysts results in complete isolation of Pt and Co in Pt-Co particles, leaving Pt and Co in supercages and sodalite cages, respectively. 

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