Mixed metal zeolite

The mixed metal zeolites were prepared according to the procedure of Scherzer and Fort (18). There were, however, several additional preparations similar to those of Scherzer and Fort that we developed. First of all, ruthenium was introduced into zeolite Y and ZSM-5 as the cationic amine complex as reported by Jacobs and Uytterhoeven (19). Ruthenium was also added to the zeolite in an anionic complex form, either K Ru N) or K2Ru(CN) N0. For these anionic preparations, either copper, zinc or cobalt exchanged zeolites Y or ZSM-5 were used. 

The Fe(C0)5, (C Hj Fe and mixed metal zeolites were reduced in hydrogen in our in-situ Mossbauer cell between temperatures of 300°C and 500°C for various times, 4 hours to 25 hours, depending on the form of iron introduced into the zeolites and depending on the particular zeolite. 

The data for mixed metal zeolites as first prepared by Scherzer and Fort (18) shown in Tables I and XI are quite extensive. The reported isomer shifts and quadrupole splittings are for the iron atoms in the anionic state. Each of these unreduced samples show Mossbauer spectra that are in close agreement with literature values of the corresponding iron coordination complexes. Typical examples of unreduced and reduced samples are shown in Figures 3 and 4. We note here that preparations 16 through 22 are new and are developments of our laboratory and that 9 through 15 are preparations based on the work of Scherzer and Fort (18). Samples 16 and 17 show that this method can be extended to other zeolites like ZSM-5. If no transition metal cation is used in the synthesis, no Mossbauer spectrum for the corresponding anion is observed. Therefore, the nature of the cation is critical and complexation of the anion to a cation is necessary for anion inclusion. Certain transition metal cations (Ru + for instance) do not seem to bind the anion. 

Catalysis by Metal Oxides and Zeolites. Metal oxides are common catalyst supports and catalysts. Some metal oxides alone are industrial catalysts an example is the y-Al202 used for ethanol dehydration to give ethylene. But these simple oxides are the exception mixed metal oxides are more... 

For cationic zeolites Richardson (79) has demonstrated that the radical concentration is a function of the electron affinity of the exchangeable cation and the ionization potential of the hydrocarbon, provided the size of the molecule does not prevent entrance into the zeolite. In a study made on mixed cationic zeolites, such as MgCuY, Richardson used the ability of zeolites to form radicals as a measure of the polarizing effect of one metal cation upon another. He subsequently developed a theory for the catalytic activity of these materials based upon this polarizing ability of various cations. It should be pointed out that infrared and ESR evidence indicate that this same polarizing ability is effective in hydrolyzing water to form acidic sites in cationic zeolites (80, 81). 

The applications of IR spectroscopy in catalysis are many. For example, IR can be used to directly characterize the catalysts themselves. This is often done in the study of zeolites, metal oxides, and heteropolyacids, among other catalysts [77,78], To exemplify this type of application, Figure 1.11 displays transmission IR spectra for a number of Co Mo O (0 < x < 1) mixed metal oxides with various compositions [79]. In this study, a clear distinction could be made between pure Mo03, with its characteristic IR peaks at 993, 863, 820, and 563 cm-1, and the Mo04 tetrahedral units in the CoMo04 solid solutions formed upon Co304 incorporation, with its new bands at 946 and 662 cm-1. These properties could be correlated with the activity of the catalysts toward carburization and hy-drodenitrogenation reactions. 

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... 

In our experiments we screened zeolites, ion-exchange resins, heteropoly compounds and mixed metal oxides. Several alcohols were used to show the range of applicability. The selectivity was assessed by testing the formation of side products in a suspension of catalyst in alcohol (e.g. SZ in 2-ethylhexanol) under reflux for 24 hours. Under the reaction conditions, no by-products were detected by GC analysis. 

Immobilized nitrile hydratase Mixed metal oxides Zeolites, SAPO Zeolite... 

To improve process economics, further work is needed to improve catalyst lifetimes. A more stable system employed a noble metal-loaded potassium L-zeolite catalyst for the condensation of ethanol with methanol to produce a 1-propanol and 2-methyl-l-propanol (US patent no. 5,300,695) (18). However, yields were small compared with the large amounts of CO and C02 produced from the methanol. More recently, Exxon patented a noble metal-loaded alkali metal-doped mixed metal (Zr, Mn, Zn) oxide (US patent nos. 6,034,141 and 5,811,602) (19,20). The catalyst was used in a syngas atmosphere. As with other catalysts, the higher temperatures resulted in decomposition of methanol. Changes in catalyst composition were noted at higher temperatures, but the stability of the catalyst was not discussed. Recently, compositions including Ni, Rh, Ru, and Cu were investigated (21,22). 

These mixed metal systems have also been tested with the transient method for catalytic activity in the Fischer-Tropsch reaction. We would like to remark here that the nature of the cation, anion, and zeolite are all important factors in the Fischer-Tropsch reactions that we have studied. Further details of these catalytic studies can be found elsewhere (23). We do observe here, however, that some catalysts that are completely reduced to the metallic state are not necessarily the most active catalysts. Also, even though the Mossbauer experiments suggest that 400°C is sufficient for complete reduction, higher activation temperatures can increase the activity and selectivity of these reactions. We have also observed that the cation definitely changes the product distribution and the activity. 

Zinc siloxides derived from Si-OH species have received considerable attention in recent years, since they can be used as precursors for metal silicates and mixed-metal oxide systems as well as for models for heterogeneous silica-supported catalytic systems and complex zeolite systems. 

The use of zeolites and zeotypes for selective oxidation reactions is a relatively new development. Classic selective oxidation catalysts are mixed-metal oxides with relatively low surface areas and good dispersion of the various active components. 

Supported metal oxide catalysts are a new class of catalytic materials that are excellent oxidation catalysts when redox surface sites are present. They are ideal catalysts for investigating catalytic molecular/electronic structure-activity selectivity relationships for oxidation reactions because (i) the number of catalytic active sites can be systematically controlled, which allows the determination of the number of participating catalytic active sites in the reaction, (ii) the TOP values for oxidation studies can be quantitatively determined since the number of exposed catalytic active sites can be easily determined, (iii) the oxide support can be varied to examine the effect of different types of ligand on the reaction kinetics, (iii) the molecular and electronic structures of the surface MOj, species can be spectroscopically determined under all environmental conditions for structure-activity determination and (iv) the redox surface sites can be combined with surface acid sites to examine the effect of surface Bronsted or Lewis acid sites. Such fundamental structure-activity information can provide insights and also guide the molecular engineering of advanced hydrocarbon oxidation metal oxide catalysts such as supported metal oxides, polyoxo metallates, metal oxide supported zeolites and molecular sieves, bulk mixed metal oxides and metal oxide supported clays. 

A reaction that is catalyzed by a Bronsted acid site, or H, can often be accelerated by addition of a solid acid. Materials like ion-exchange resins, zeolites, and mixed metal oxides function as solid analogues of corrosive liquid acids (e.g., H2SO4 and HF) and can be used as acidic catalysts. For example, isobutylene (IB) reacts with itself to form dimers on cross-linked polyfstyrene-sulfonic acid), a strongly acidic solid polymer catalyst ... 

Another major reason for studying mixed metal oxide membranes from double metal alkoxides is the potential for preparing zeolite>like membranes which can exhibit not only separation but also catalytic properties. It has been suggested that combinations of silica and alumina in a membrane could impart properties similar to those of natural and synthetic zeolites [Anderson and Chu, 1993]. Membranes with a pore diameter of 10 to 20 nm and consisting of combinations of titania, alumina and silica have been demonstrated by using a mixture of a meta>titanic acid sol, an alumina sol and silicic acid fine particles followed by calcining at a temperature of 500 to 900 C [Mitsubishi Heavy Ind., 1984d]. 

In addition to practical applications, metal cluster-derived catalysts, particularly intrazeolite metal cluster compounds, may aid in the identification of catalytically important bonding and structural patterns and thereby further our molecular understanding of surface science and heterogeneous catalysis. The ship-in-bottle technique for the synthesis of bulky metal-mixed metal cluster compounds inside zeolites and/or interlayered minerals has gained growing attention for the purpose of obtaining catalytic precursors surrounded by the interior constraint, imposing molecular shape selectivity. Such approaches may pave the way to offer the molecular architecture of hybrid (multifunctional) tailored catalysts to achieve the desired selectivity and stability for industrial processes. 

Recently, great attention has been paid to the ambient temperature adsorption for removing sulfur compounds from natural gas, as the system is simple and is quick and easy to be started up. The major adsorbents that were used in the ambient temperature adsorption are AC-based and zeolite-based materials. The Osaka Gas mixed metal and metal oxide catalyst provides a low-temperature method of desulfurization. The catalysts (or adsorbents) is claimed to remove organic sulfur and H2S at room temperature.115... 

Of course, more complex systems also exist (see Figure 9.6). Although there is no evidence for the existence of mixed metal clusters as yet, ESR signals show that there might be interactions between sodium and cesium clusters in zeolites. 

The various processes for the catalytic reaction are similar. The factor that makes the difference is the choice of catalyst, which in turn affects the temperature regime needed to trigger the decomposition of nitrous oxide. In the literature, numerous works illustrate the several classes of catalysts appropriate for this reaction [9a, k] noble metals (Pt, Au), pure or mixed metal oxides (spinels, perovskite-types, oxides from hydrotalcites), supported systems (metal or metal oxides on alumina, silica, zirconia) and zeolites. 

Metal oxides are widely used as catalyst supports but can also be catalytically active and useful in their own right. Alumina, for example, is used to manufacture ethene from ethanol by dehydration. Very many mixed metal oxide catalysts are now used in commercial processes. The best understood and most interesting of these are zeolites that offer the particular advantage of shape selectivity resulting from their narrow microporous pore structure. Zeolites are now used in a number of large-scale catalytic processes. Their use in fine chemical synthesis is discussed in Chapter 2. 

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