A link between reactivity and local structure in acid catalysis on zeolites

The extent to which spatial constraints influence rates and pathways in catalysis depends on the structure of intermediates, transition states, and active sites involved. We aim to answer, as we seek insights into catalytic mechanisms and site requirements, persistent questions about the potential for controlling rates and selectivities by rational design of spatial constraints around active sites within inorganic structures useful as catalysts. This Account addresses these matters for the specific case of reactions on zeolites that contain Br?nsted acid sites encapsulated within subnanometer channels. We compare and contrast here the effects of local zeolite structure on the dynamics of the carbonylation of surface methyl groups and of the isotopic exchange of CD4 with surface OH groups on zeolites. Methyl and hydroxyl groups are the smallest monovalent cations relevant in catalysis by zeolites. Their small size, taken together with their inability to desorb except via reactions with other species, allowed us to discriminate between stabilization of cationic transition states and stabilization of adsorbed reactants and products by spatial constraints. We show that apparent effects of proton density and of zeolite channel structure on dimethyl ether carbonylation turnover rates reflect instead the remarkable specificity of eight-membered ring zeolite channels in accelerating kinetically relevant steps that form *COCH3 species via CO insertion into methyl groups. This specificity reflects the selective stabilization of cationic transition states via interactions with framework oxygen anions. These findings for carbonylation catalysts contrast sharply the weak effects of channel structure on the rate of exchange of CD4 with OH groups. This latter reaction involves concerted symmetric transition states with much lower charge than that required for CH3 carbonylation. Our Account extends the scope of shape selectivity concepts beyond those reflecting size exclusion and preferential adsorption. Our ability to discriminate among various effects of spatial constraints depends critically on dissecting chemical conversions into elementary steps of kinetic relevance and on eliminating secondary reactions and accounting for the concomitant effects of zeolite structure on the stability of adsorbed reactants and intermediates.     

Gallium-loaded zeolites for light paraffin aromatization: evidence for exchanged gallium cation active centers

It is shown that certain metal-loaded zeolites (e.g., Ga-MFI) initially prepared as separate metal-containing and zeolite phases are reducible, resulting in solid-state transfer of the metal to the zeolite. The final material is similar to those initially prepared as ‘unsegregated’ by methods such as aqueous impregnation. Reduction occurs either through appropriate pretreatment or onstream in certain hydrocarbon reactions. First, preparation methods leading to one or the other type of material are examined. Then it is shown that reduced catalysts give far higher ratios of dehydrogenation to cracking rates (for alkanes) than either segregated or unsegregated but unreduced systems. The product distributions of the propane reaction at low partial pressure and low conversion are also reviewed, and new data presented for unsegregated, reduced catalysts. There are great differences in the distribution obtained using reduced 1/1 metal/A1 catalysts from corresponding distributions for the H-form zeolites or for segregated systems. The differences suggest a mechanism which may be entirely independent of catalysis by protons.     

Unifying Principles in Zeolite Chemistry and Catalysis

In recent years molecular sieve catalysts have assumed an increasingly important role in industrial catalysis, Applications of zeolite catalysts are expanding from the traditional petroleum refining to new and improved fuel processing applications, and to new roles in both the petrochemical and chemical industries. Up to the present, all commercial applications of zeolite catalysts have been carried out with aciaic zeolites. Recent investigations of zeolite chemistry revealed several important features which appear common to both alkali and acidic zeolites. This new chemical evidence raises the possibility that the underlying physicochemical features of both types of zeolites play a role in catalysis.     

Mesoporous zeolite single crystal catalysts: Diffusion and catalysis in hierarchical zeolites

During the last years, several new routes to produce zeolites with controlled mesoporosity have appeared. Moreover, an improved catalytic performance of the resulting mesoporous zeolites over conventional zeolites has been demonstrated in several reactions. In most cases, the mesoporous zeolites exhibit higher catalytic activity, but in some cases also improved selectivity and longer catalyst lifetime has been reported. The beneficial effects of introducing mesopores into the zeolites has in most instances been attributed to improved mass transport to and from the active sites located in the zeolite micropores. Here, we briefly discuss the most important ways of introducing mesopores into zeolites and, for the first time, we show experimentally that the presence of mesopores dramatically increases the rate of diffusion in zeolite catalysts. This is done by studying the elution of iso-butane from packed beds of conventional and mesoporous zeolite catalysts. Moreover, we discuss in detail the recent observation of improved activity and selectivity in the alkylation of benzene with ethene using mesoporous zeolite single crystal catalysts. For this reaction, we show by calculation of the Thiele modulus that this improved performance can be mainly attributed to a diffusional limitation of ethylbenzene in the zeolite pores. This is verified in new ethylbenzene dealkylation experiments where mesoporous zeolite catalysts show significantly improved activity over conventional zeolite catalysts.     

Unifying Principles in Zeolite Chemistry and Catalysis

Abstract

In recent years molecular sieve catalysts have assumed an increasingly important role in industrial catalysis, Applications of zeolite catalysts are expanding from the traditional petroleum refining to new and improved fuel processing applications, and to new roles in both the petrochemical and chemical industries. Up to the present, all commercial applications of zeolite catalysts have been carried out with aciaic zeolites. Recent investigations of zeolite chemistry revealed several important features which appear common to both alkali and acidic zeolites. This new chemical evidence raises the possibility that the underlying physicochemical features of both types of zeolites play a role in catalysis.     

Production of methylamines over ZK-5 zeolite treated with tetramethoxysilane

The reaction of methonol with ammonia over catalysts, used commercially today, to give methylamines, does not occur with the desired dimethylamine selectivity. Both a thermodynamically and kinetically controlled reaction over conventional catalysts permits a maximum dimethylamine selectivity (DMA selectivity) of only about 30 mol-%. In addition to monomethylamine (MMA), a large amount of the undesirable trimethylamine (TMA) is formed. By using zeolites and taking advantage of their shap-selective properties, it is possible to achieve high MMA and DMA selectivities. Shape-selective catalysis can only take place at catalytically active centrs in the inteerior of the por system. The proportion of non-shape-selective catalysis at the active centres on the outer surfaces of zeolites is not negligible. Treatment of ZK-5 zeolite with tetramethoxysilane deactivates the outer surface of the crystallite and increases the shape-selectivity of the ZK-5 zeolite with rgard to the amination reaction. Computer simulation of the zeolite skeleton in conjuction with investigations of the reaction leads to some conclusions with respect to the reaction mechanisms and reaction sites.     

Molecular models of catalytically active sites in zeolites. Quantum chemical approach

A brief review of quantum chemical studies of different active sites in zeolites is presented. Various factors that significantly affect the strength of Brønsted acid sites in zeolites are discussed. An interaction of zeolite protons with entrapped metal particles is considered as a reason of electron-deficiency of metal clusters in zeolite cavities on the Pd and Pt species as an example. Probable precursors of Lewis acid sites (LAS) and reliable molecular models of the LAS in zeolites are discussed on the basis of quantum chemical analysis. Transition metal ions can be catalytically active in the lattice or extra-lattice zeolite positions and the two possibilities are considered for selective oxidation site in titanium silicalite and FeZSM-5 zeolite catalysts, respectively.     

Synthesis of Dihydropyrimidinones Using Large Pore Zeolites

Abstract  

A series of dihydropyrimidin-2(1H)-one (DHPM) belongs to one of the important class of therapeutic and pharmacological active compound, were synthesized through the multicomponent reactions (MCRs) of aldehydes, ethyl acetoacetate and urea, followed by the heterogeneous catalyzed Biginelli reaction. In the present endeavour, medium (ZSM-5) and large pore zeolites (Y, BEA and MOR) as well as dealuminated zeolites BEA, were studied as catalysts. An excellent activity for DHPMs synthesis is achieved by optimizing accessibility of the reactants to the active sites and the surface polarity of zeolite catalysts. Moreover, the mechanism of Biginelli reaction was studied by means of GAUSSVIEW energy calculations of adsorbed acylimine intermediate on zeolite by using the density functional method (DFT).     

The synthetic strategies of hierarchical TS-1 zeolites for the oxidative desulfurization reactions

With the increasingly stringent standards for limiting sulfide content in liquid fuels, oxidative desulfurization (ODS) has become a promising ultra-deep desulfurization process in fuel desulfurization. TS-1 zeolites show great potential as catalysts for ODS reactions, due to its remarkable oxidation activity at low temperatures and pressure. However, the inherent microporous structure of conventional TS-1 zeolites restricts the mass transportation and renders the active sites in the microporous space of TS-1 zeolites inaccessible for bulky aromatic organosulfur compounds. Fabrication of hierarchical TS-1 zeolites by incorporating meso-/macropores into microporous TS-1 zeolites is an effective strategy to improve mass transportability. In recent years, abundant efforts have been dedicated to developing synthetic strategies of hierarchical TS-1 zeolite, thereby improving its catalytic performance in the ODS process. This mini-review addresses the synthetic methods of hierarchical TS-1 catalysts and their catalytic performance in the ODS reactions. In addition, some current problems and prospects of synthesis routes for constructing hierarchical TS-1 catalysts have also been revised. We expect this mini-review to shed light on the more efficient preparation strategies of hierarchical TS-1 zeolites for the ODS process.     

The synthetic strategies of hierarchical TS-1 zeolites for the oxidative desulfurization reactions

With the increasingly stringent standards for limiting sulfide content in liquid fuels, oxidative desulfurization (ODS) has become a promising ultra-deep desulfurization process in fuel desulfurization. TS-1 zeolites show great potential as catalysts for ODS reactions, due to its remarkable oxidation activity at low temperatures and pressure. However, the inherent microporous structure of conventional TS-1 zeolites restricts the mass transportation and renders the active sites in the microporous space of TS-1 zeolites inaccessible for bulky aromatic organosulfur compounds. Fabrication of hierarchical TS-1 zeolites by incorporating meso-/macropores into microporous TS-1 zeolites is an effective strategy to improve mass transportability. In recent years, abundant efforts have been dedicated to developing synthetic strategies of hierarchical TS-1 zeolite, thereby improving its catalytic performance in the ODS process. This mini-review addresses the synthetic methods of hierarchical TS-1 catalysts and their catalytic performance in the ODS reactions. In addition, some current problems and prospects of synthesis routes for constructing hierarchical TS-1 catalysts have also been revised. We expect this mini-review to shed light on the more efficient preparation strategies of hierarchical TS-1 zeolites for the ODS process.     

Perspectives of Micro/Mesoporous Composites in Catalysis

This article covers the recent development in the remarkably growing field of synthesis, characterization and particularly catalytic investigation of zeolite‐based materials combining micro‐ and mesoporous features. New synthetic approaches for preparation of micro/mesoporous composites including recrystallization of originally amorphous matter, utilization of nanocrystalline zeolite seeds and formation of mesoporous zeolite single crystals are the first focus of this article. The advantages and disadvantages of composite materials in comparison with pure micro‐ and mesoporous molecular sieves will be discussed, as well. The relevance of individual experimental techniques for analysis of the composites, i.e., their structure, porosity, chemical composition, morphological features, and so on, are described in the second section of the article. The last Section is focused on the application of micro/mesoporous composites and mesoporous zeolites as catalysts in acid‐catalyzed reactions, oxidation reactions and synthesis of fine chemicals. The potential of the composites in challenging areas of catalysis for future applications is the final objective of the review.     

Perspectives of Micro/Mesoporous Composites in Catalysis

This article covers the recent development in the remarkably growing field of synthesis, characterization and particularly catalytic investigation of zeolite-based materials combining micro- and mesoporous features. New synthetic approaches for preparation of micro/mesoporous composites including recrystallization of originally amorphous matter, utilization of nanocrystalline zeolite seeds and formation of mesoporous zeolite single crystals are the first focus of this article. The advantages and disadvantages of composite materials in comparison with pure micro- and mesoporous molecular sieves will be discussed, as well. The relevance of individual experimental techniques for analysis of the composites, i.e., their structure, porosity, chemical composition, morphological features, and so on, are described in the second section of the article. The last Section is focused on the application of micro/mesoporous composites and mesoporous zeolites as catalysts in acid-catalyzed reactions, oxidation reactions and synthesis of fine chemicals. The potential of the composites in challenging areas of catalysis for future applications is the final objective of the review.     

The strong basicity of the microporous titanosilicate ETS-10

Base-catalysed reactions in general are of great importance. In zeolite chemistry, alkali-metal-exchanged zeolites, such as zeolite X, display very strong basicity coupled with high catalytic activity. However, in order to achieve this strong basicity, considerable post-synthesis modification is necessary. In this report, it is shown that strong basicity is exhibited by the microporous titanosilicate ETS-10 in the as-prepared form which is superior to the presently known suite of zeolite catalysts. This opens up a new class of material for heterogeneous base catalysis. This revised version was published online in August 2006 with corrections to the Cover Date.     

The Formation,Characterization, and Catalytic Activity of Transition Metal Complexes in Zeolites: The P. H. Emmett Award Address

The chemistry of transition metal complexes in zeolites has received considerable attention in our laboratory because we believe that such complexes have potential both in fundamental and applied catalysis. To scientists outside of the field of heterogeneous catalysis it often appears virtually hopeless to obtain meaningful chemistry from surface reactions because the active centers are so poorly characterized. Although most catalytic chemists would not totally agree with this viewpoint, one would have to admit that it contains an element of truth. The traditional approach to solving this problem has been to attempt better characterization of active sites on known catalysts, and while some significant advances have been made in this direction, the progress in general has been painfully slow. Another approach, and the one which will be described here, has been to synthesize surface complexes which are both well defined and active as catalysts. These then may serve as model systems for conventional catalysts, but more than this, they may be unique catalysts which are important in their own right.     

The Formation, Characterization, and Catalytic Activity of Transition Metal Complexes in Zeolites: The P. H. Emmett Award Address

The chemistry of transition metal complexes in zeolites has received considerable attention in our laboratory because we believe that such complexes have potential both in fundamental and applied catalysis. To scientists outside of the field of heterogeneous catalysis it often appears virtually hopeless to obtain meaningful chemistry from surface reactions because the active centers are so poorly characterized. Although most catalytic chemists would not totally agree with this viewpoint, one would have to admit that it contains an element of truth. The traditional approach to solving this problem has been to attempt better characterization of active sites on known catalysts, and while some significant advances have been made in this direction, the progress in general has been painfully slow. Another approach, and the one which will be described here, has been to synthesize surface complexes which are both well defined and active as catalysts. These then may serve as model systems for conventional catalysts, but more than this, they may be unique catalysts which are important in their own right.     

Etherification on Zeolites: MTBE synthesis

Although the use of methyl-tert butyl ether (MTBE) in reformulated gasoline has raised concerns due to its detection in ground water and has led to its gradual phase out in parts of the United States, the use of heavier ethers in gasoline in the future is possible. The synthesis of MTBE provides us with an insight into etherification reactions in general. This article reviews the extensive findings over the past 15 years on the application of acidic zeolites as alternative catalysts for etherification reactions and, in particular, MTBE synthesis, and compares the results with those of the commercially used ion-exchange resins. Although the resin catalysts are very active, they have some significant drawbacks (i.e., thermal fragility, sensitivity to methanol/isobutene ratios, and corrosive/disposal problems). Zeolites have been considered to be potential alternative catalysts for MTBE synthesis due to their excellent properties such as high thermal stability and modifiable acidity. The impact of various zeolite parameters, such as Si/Al ratio, type of zeolite, and the presence of extra-lattice Al, on activity is explored. Although the specific activities of most zeolites have been found to be too low to compete at low temperatures required to avoid thermodynamic limitations, H-beta zeolite has been found to be as active as the current commercial resin catalysts being used for MTBE synthesis. In addition, all zeolites studied have been found to have high selectivities to MTBE and low sensitivities to methanol/isobutene molar ratio, permitting the use of the stoichiometric reactant ratio. Application of zeolites for the synthesis of higher ethers is suggested.     

Etherification on Zeolites: MTBE synthesis

Although the use of methyl-tert butyl ether (MTBE) in reformulated gasoline has raised concerns due to its detection in ground water and has led to its gradual phase out in parts of the United States, the use of heavier ethers in gasoline in the future is possible. The synthesis of MTBE provides us with an insight into etherification reactions in general. This article reviews the extensive findings over the past 15 years on the application of acidic zeolites as alternative catalysts for etherification reactions and, in particular, MTBE synthesis, and compares the results with those of the commercially used ion-exchange resins. Although the resin catalysts are very active, they have some significant drawbacks (i.e., thermal fragility, sensitivity to methanol/isobutene ratios, and corrosive/disposal problems). Zeolites have been considered to be potential alternative catalysts for MTBE synthesis due to their excellent properties such as high thermal stability and modifiable acidity. The impact of various zeolite parameters, such as Si/Al ratio, type of zeolite, and the presence of extra-lattice Al, on activity is explored. Although the specific activities of most zeolites have been found to be too low to compete at low temperatures required to avoid thermodynamic limitations, H-beta zeolite has been found to be as active as the current commercial resin catalysts being used for MTBE synthesis. In addition, all zeolites studied have been found to have high selectivities to MTBE and low sensitivities to methanol/isobutene molar ratio, permitting the use of the stoichiometric reactant ratio. Application of zeolites for the synthesis of higher ethers is suggested.     

Alcohol Reactivity on Zeolites and Molecular Sieves

Zeolites and molecular sieves have been extensively studied and applied in different fields. Their specific crystalline structure and composition make it possible to obtain high-activity stable catalyst systems for a wide range of chemical reactions. There are many investigations on the structural characteristics and adsorption and catalytic properties of zeolites and molecular sieves as well as on the relation between the different properties. The nature of active sites in zeolite catalysts and the mechanism of catalytic processes on their surface belong to the most important problems of the investigations.     

Fluorine-Promoted Catalysts

Abstract

It has been recognized for some time that the incorporation of fluorine in oxide catalysts (for example, alumina, silica-alumina, or zeolites) enhances their activity for acid-catalyzed reactions such as cracking, isomerization, alkylation, polymerization, and disproportionation. These reactions are thought to proceed via carbocation intermediates which are formed and stabilized on surface protonic sites. The incorporation of fluorine increases the activity by enhancing the acidic properties of the catalyst. Fluorine incorporated in an oxide catalyst replaces surface O or OH, and because fluorine is very electronegative, it polarizes the lattice more than the groups it replaces, and this increases the acidity of both protonic (Brönsted) and nonprotonic (Lewis) sites on the surface. As will be seen, pure alumina is inactive or only slightly active for acid-catalyzed reactions. In contrast, it has been shown repeatedly that fluorinated alumina is a very active, selective, and stable catalyst for such reactions. The formation of fluorinated solid “superacids” which are active catalysts at low temperatures also has been reported. Very recently fluorination has been used in the modification of zeolite catalysts for better activity.