Zeolite catalysts molecular structure

Catalytic oxidative dehydrogenation of propane by N20 (ODHP) over Fe-zeolite catalysts represents a potential process for simultaneous functionalization of propane and utilization of N20 waste as an environmentally harmful gas. The assumed structure of highly active Fe-species is presented by iron ions balanced by negative framework charge, mostly populated at low Fe loadings. These isolated Fe sites are able to stabilize the atomic oxygen and prevent its recombination to a molecular form, and facilitate its transfer to a paraffin molecule [1], A major drawback of iron zeolites in ODHP with N20 is their deactivation by accumulated coke, leading to a rapid decrease of the propylene yield. 

In the following decades, researchers in catalysis turned their efforts to controlhng molecular structure as well as size. The catalyst zeolite paved the way. In the late 1960s, researchers at Mobil Oil Co. were able to s)uithesize zeolite by deliberately designing and preparing the structure of catalysts at the atomic and molecular levels. The resulting nanostructured crystalline material (ZSM-5)—with a 10-atom ring and pore size of 0.45-0.6 nm—enabled the control of selectivity in petrochemical processes at the... 

Zeolite catalysts play a vital role in modern industrial catalysis. The varied acidity and microporosity properties of this class of inorganic oxides allow them to be applied to a wide variety of commercially important industrial processes. The acid sites of zeolites and other acidic molecular sieves are easier to manipulate than those of other solid acid catalysts by controlling material properties, such as the framework Si/Al ratio or level of cation exchange. The uniform pore size of the crystalline framework provides a consistent environment that improves the selectivity of the acid-catalyzed transformations that form C-C bonds. The zeoHte structure can also inhibit the formation of heavy coke molecules (such as medium-pore MFl in the Cyclar process or MTG process) or the desorption of undesired large by-products (such as small-pore SAPO-34 in MTO). While faujasite, morden-ite, beta and MFl remain the most widely used zeolite structures for industrial applications, the past decade has seen new structures, such as SAPO-34 and MWW, provide improved performance in specific applications. It is clear that the continued search for more active, selective and stable catalysts for industrially important chemical reactions will include the synthesis and application of new zeolite materials. 

In recent years, modification of zeolites, such as HZSM-5, by phosphoric compounds or metal oxides has been extensively studied, but little information is available on the modification of zeolites by diazomethane, which is an excellent methylating agent for protonic acidic sites. It is capable of entering into the small pores of zeolites because of its small molecular size and linear molecular structure. Yin and Peng (1,2) reported that the acidity and specific surface area of the inorganic oxide supports (AljOs, SiOj) and zeolite catalysts... 

The paper deals with some new data concerning the state of the metal after reduction and the catalytic functions of zeolite catalysts containing nickel and platinum. By using the molecular sieve selectivity in the hydrogenation of mesitylene it has been proved that metal (platinum) is contained in the volume of the zeolite crystal. The temperature dependence of the formation of nickel crystals was investigated. The aluminosilicate structure and the zeolite composition influence mainly the formation of the metal surface which determines the catalytic activity. In the hydrocracking of cumene and disproportionation of toluene a bifunctional action of catalysts has been established. Hydrogen retarded the reaction. 

In principle, all the kinetic concepts of intercalation introduced for layer-structured silicates hold for zeolites as well. Swelling, of course, is not found because of the rigidity of the three dimensional frame. The practical importance of zeolites as molecular sieves, cation exchangers, and catalysts (cracking and hydrocracking in petroleum industry) is enormous. Molecular shape-selective transport (large differences in diffusivities) and micro-environmental catalysis (in cages and channels)... 

Zeolitic Catalyst—Since the early 1960s. modern cracking catalysts contain a silica-alumina crystalline structured material called zeolite. This zeolite is commonly called a molecular sieve. The admixture of a molecular sieve in with the base clay matrix imparts desirable cracking selectivities. 

Zeolite catalysts may also be regarded as mixed oxides, but the crystallographic structures differ from the solids discussed above in that active sites for catalysis occur within the open lattice framework. In consequence, rate data are not directly comparable with similar observations for other heterogeneous reactions since the preexponential factors are calculated and reported on a different basis. For completeness, however, it is appropriate to mention here that instances of compensation behavior on zeolite catalysts are known. Taylor and Walker (282) described such an effect for the decomposition reactions of formic acid and of methyl forma te on cation-exchanged 13X molecular sieves, and comparable trends may be found in data reported for reactions of propene on similar catalysts (283). 

The reductive/oxidative properties of transitional metal elements in these zeolite catalysts were also examined by TPR and TPO, and it is shown that metallic species in certain cation locations may migrate under calcination, reduction, and reaction conditions [7], The different treatment, e g, coking or even the oxidative regeneration, will produce metallic species of varied oxidation states with different distributions in the molecular sieve structures as exemplified by the above XPS data. The redox properties of these metallic cations exhibit the influence of hydrogen and/or coke molecules, and it is further postulated that the electron transfer with oxygen species are considered responsible for their catalyzed performance in the TPO regeneration processes, as shown in Figure 2. 

There have been few Raman investigations of catalyst preparation (of oxides, zeolites, or metals). Such experiments deliver information about molecular structures, and the formation of crystalline phases is detected at earlier stages by Raman spectroscopy than by XRD. Moreover, cells that allow for variable conditions are easily constructed. 

CONTENTS Introduction, Thom H. Dunning, Jr. Electronic Structure Theory and Atomistic Computer Simulations of Materials, Richard P. Messmer, General Electric Corporate Research and Development and the University of Pennsylvania. Calculation of the Electronic Structure of Transition Metals in Ionic Crystals, Nicholas W. Winter, Livermore National Laboratory, David K. Temple, University of California, Victor Luana, Universidad de Oviedo and Russell M. Pitzer, The Ohio State University. Ab Initio Studies of Molecular Models of Zeolitic Catalysts, Joachim Sauer, Central Institute of Physical Chemistry, Germany. Ab Inito Methods in Geochemistry and Mineralogy, Anthony C. Hess, Battelle, Pacific Northwest Laboratories and Paul F. McMillan, Arizona State University. 

Coke is formed through aromatic condensation reactions (21) which on the molecular scale are spatially quite demanding. Zeolites, with molecular-sized pore systems, tend to be significantly less prone to coke formation than ASA-based catalysts, which do not have such spatially restricted pore structures. Correspondingly, in commercial operation zeolitic catalysts tend to be significantly more stable than ASAs (see Fig. 6.5). 

In the isomerization of styrene oxides in a fixed bed reactor under gas phase conditions, the catalytic performance of various catalysts on the activity, selectivity and service time was screened at 300°C and WHSV = 2-3h" . As shown in Fig. 15.1, zeolites with MFI-structure are superior to other zeolite types and non zeolitic molecular sieves, as well as greatly superior to amorphous metal oxides. 

Theoretical modeling of the structure and reactivity of zeolitic materials, with special emphasis on the mechanism of catalytic reactions, has been the subject of several exhaustive review articles in the past decade. Theoretical approaches that have been used to describe such systems range from empirical molecular mechanics calculations to various ab initio methods as well as different variants of the mixed quantum/classical (QM/MM) algorithms. In the present contribution we focus our attention mainly on those studies which were accomplished by ab initio pseudopotential plane wave density functional methods that are able to treat three-dimensional periodic models of the zeolite catalysts. Where appropriate, we attempt a critical comparison of with other theoretical approaches. 

The driving force behind the rapid development of powder diffraction methods over the past 10 years is the increasing need for structural characterization of materials that are only available as powders. Examples are zeolite catalysts, magnets, metal hydrides, ceramics, battery and fuel cell electrodes, piezo- and ferroelectrics, and more recently pharmaceuticals and organic and molecular materials as well as biominerals. The emergence of nanoscience as an interdisciplinary research area will further increase the need for powder diffraction, pair-distribution function (PDF) analysis of powder diffraction pattern allows the refinement of structural models regardless of the crystalline quality of the sample and is therefore a very powerful structural characterization tool for nanomaterials and disordered complex materials. 

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. 

Since their discovery, microporous materials such as zeolites found major application fields in processes like separation, ion exchange and catalysis. Their uniform pore size and pore architecture are at the basis of separation processes whereas the chemical composition of these materials makes them unbeatable candidates to be used as a catalyst or an ion exchanger. Regardless of which process is used, the molecules engaged are adsorbed on the surface according to their molecular structure and properties. The bulkiness of the molecule compared to the pore size of the microporous material decides if or not the molecule can be trapped in the depth of the porous framework, thus there exists cases where molecules with larger diameters than the pore size are not able to enter the pores. This makes the microporous materials acting as a sieve in molecular level and they are hence referred to as molecular sieves. 

Catalysts based on molecular sieve zeolites will certainly continue to be of much interest in petroleum refining. Improvements can be expected as time goes on. Radically different zeolite structures offer the most chance of major improvements. Several authors have indicated the likelihood of obtaining radical, carbanion, and other noncarbonium ion reactions over zeolite catalysts. Pursuit of this possibility may prove fruitful. 

Over the past My years there have beat significant developments in the synthesis of zeolites of different pore sizes [6], Many of these developments have resulted in new applications of zeolite catalysts for petrochemical processes. TM is eq>eciaHy so, for exauqile, in the case of catafytic cracking whidi ideally requires the pore sizes to be tailored to cater for reactions involving a wide range of molecular sizes thus leading to the syntheas of catalysts with macro-, meso- and micropores. Table 1 shows the pore aze, dimensionality and structure type of some of the zeolites and molecular aeves which will be discussed in this paper. 

The incorporation of Ti into various framework zeolite structures has been a very active research area, particularly during the last 6 years, because it leads to potentially useful catalysts in the oxidation of various organic substrates with diluted hydrogen peroxide [1-7]. The zeolite structures, where Ti incorporation has been achieved are ZSM-5 (TS-1) [1], ZSM-11 (TS-2) [2] ZSM-48 [3] and beta [4]. Recently, mesoporous titanium silicates Ti-MCM-41 and Ti-HMS have also been reported [5]. TS-1 and TS-2 were found to be highly active and selective catalysts in various oxidation reactions [6,7]. All other Ti-modified zeolites and molecular sieves had limited but interesting catalytic activities. For example, Ti-ZSM-48 was found to be inactive in the hydroxylation of phenol [8]. Ti-MCM-41 and Ti-HMS catalyzed the oxidation of very bulky substrates like 2,6-di-tert-butylphenol, norbomylene and a-terpineol [5], but they were found to be inactive in the oxidation of alkanes [9a], primary amines [9b] and the ammoximation of carbonyl compounds [9a]. As for Ti-P, it was found to be active in the epoxidation of alkenes and the oxidation of alkanes and alcohols [10], even though the conversion of alkanes was very low. Davis et al. [11,12] also reported that Ti-P had limited oxidation and epoxidation activities. In a recent investigation, we found that Ti-P had a turnover number in the oxidation of propyl amine equal to one third that of TS-1 and TS-2 [9b]. As seen, often the difference in catalytic behaviors is not attributable to Ti sites accessibility. 

More than one decade ago we have reported an ESR study on the molecular motion of NO2 adsorbed on porous Vycor glass [8,9] and it was found that the NO2 adsorbed on the Vycor glass and Cu-metal supported on Vycor glass gave strongly temperature-dependence ESR spectra. The present study aimed to further apply our dynamic ESR technique to elucidate motional dynamics of NO2 adsorbed on various zeolite with different structures. The results can provide fundamental and useful information which are required to develop new active catalyst and to clarify the reaction mechanism. 

The supported clusters described in this chapter have strong connections to industrial supported metal catalysts, although the clusters or particles in industrial catalysts are much less uniform and less susceptible to incisive structural characterization than those considered here. Development and further investigation of structurally simple oxide- and zeolite-supported molecular catalysts will provide fundamental understanding of structure-activity relationships that will direct design of novel and improved industrial supported metal catalysts. 

Strength (FLS) empirical approach are discussed in Section 3 as methods for determining the molecular structures of metal-oxide species from their Raman spectra. The state-of-the-art in Raman instrumentation as well as new instrumental developments are discussed in Section 4. Sampling techniques typically employed in Raman spectroscopy experiments, ambient as well as in situ, are reviewed in Section S. The application of Raman spectroscopy to problems in heterogeneous catalysis (bulk mixed-oxide catalysts, supported metal-oxide catalysts, zeolites, and chemisorption studies) is discussed in depth in Section 6 by selecting a few recent examples from the literature. The future potential of Raman spectroscopy in heterogeneous catalysis is discussed in the fmal section. 

As most of the acid sites are located in pores of molecular size the rate and the selectivity of catalytic reactions depend not only on the intrinsic properties of the sites but also on the pore structure. A zeolite catalyst selects the reactant or the product by their ability to diffuse to and from the active sites (reactant and product selectivity). Steric constraints in the environment of the sites limit or inhibit the formation of intermediates or transition states (restricted transition state selectivity) [24,25]. The strong polarizing interaction between zeolite crystallites and adsorbed molecules leads to an unusually high concentration of the reactants in the pores. This concentration effect causes an enhancement of the rates of bimolecular reaction steps over monomolecular reaction steps [26]. 

Catalyst Aging Coke Formation.—In most, possibly all, organic reactions catalysed by zeolites, high molecular weight products accumulate within the zeolite pores and deactivate the catalyst, a phenomenon distinct from deactivation due to zeolite structure modification or collapse. Under some conditions the extent of dehydrogenation of the deposit is sufficient for it to be... 

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