It is possible to say that zeolites are the most widely used catalysts in industry They are crystalline microporous materials which have become extremely successful as catalysts for oil refining, petrochemistry, and organic synthesis in the production of fine and speciality chemicals, particularly when dealing with molecules having kinetic diameters below 10 A The reason for their success in catalysis is related to the following specific features of these materials:1 (1) They have very high surface area and adsorption capacity (2) The adsorption properties of the zeolites can be controlled, and they can be varied from hydrophobic to hydrophilic type materials (3) Active sites, such as acid sites for instance, can be generated in the framework and their strength and concentration can be tailored for a particular application (4) The sizes of their channels and cavities are in the range typical for many molecules of interest (5-12 A), and the strong electric fields2 existing in those micropores together with an electronic confinement of the guest molecules3 are responsible for a preactivation of the reactants (5) Their intricate channel structure allows the zeolites to present different types of shape selectivity, ie, product, reactant, and transition state, which can be used to direct a given catalytic reaction toward the desired product avoiding undesired side reactions (6) All of these properties of zeolites, which are of paramount importance in catalysis and make them attractive choices for the types of processes listed above, are ultimately dependent on the thermal and hydrothermal stability of these materials In the case of zeolites, they can be activated to produce very stable materials not just resistant to heat and steam but also to chemical attacks Avelino Corma Canos was born in Moncofar, Spain, in 1951 He studied chemistry at the Universidad de Valencia (1967−1973) and received his PhD at the Universidad Complutense de Madrid in 1976 He became director of the Instituto de Tecnologia Quimica (UPV-CSIC) at the Universidad Politecnica de Valencia in 1990 His current research field is zeolites as catalysts, covering aspects of synthesis, characterization and reactivity in acid−base and redox catalysis A Corma has written about 250 articles on these subjects in international journals, three books, and a number of reviews and book chapters He is a member of the Editorial Board of Zeolites, Catalysis Review Science and Engineering, Catalysis Letters, Applied Catalysis, Journal of Molecular Catalysis, Research Trends, CaTTech, and Journal of the Chemical Society, Chemical Communications A Corma is coauthor of 20 patents, five of them being for commercial applications He has been awarded with the Dupont Award on new materials (1995), and the Spanish National Award “Leonardo Torres Quevedo” on Technology Research (1996) 2373 Chem Rev 1997, 97, 2373−2419

From Microporous to Mesoporous Molecular-Sieve Materials and Their Use in Catalysis

Hexagonal and cubic phases of manganese oxide mesoporous structures (MOMS) have been prepared by means of the oxidation of Mn(OH)2. The hexagonal MOMS materials form a hexagonal array of pores with an open porous structure, thick walls (1.7 nanometers), and exceptional thermal stability (1000°C). The walls of the mesopores are composed of microcrystallites of dense phases of Mn2O3 and Mn3O4, with MnO6 octahedra as the primary building blocks. The calcined hexagonal MOMS have an electrical conductivity of 8.13 × 10−6 per ohm·centimeter, an average manganese oxidation state of 3.55, and a band gap of 2.46 electron volts. Catalytic oxidations of cyclohexane and n-hexane in aqueous solutions in a batch reactor show conversions of ∼10 and ∼8 percent, respectively. Characterization and catalytic data suggest that MOMS systems show significant enhancement in thermal stability with respect to octahedral molecular sieve materials.

https://science.sciencemag.org/content/sci/276/5314/926.full.pdf

Manganese oxide mesoporous structures: Mixed-valent semiconducting catalysts

This review paper deals with proven and potential applications of mesoporous molecular sieves in catalysis. In addition to introduction and conclusion, the text is divided into two parts, respectively, dedicated to the design of solid catalysts and catalyst supports and to some relevant examples of catalytic processes.

/pdf/perspectives-in-catalytic-applications-of-mesostructured-4jgvbmynn3.pdf

Perspectives in catalytic applications of mesostructured materials

The conditions required to produce zeolites with low framework density and extra-large pores are discussed. Correlations between framework stability and geometrical and topological descriptors are presented. An attempt has been made to rationalize the synthesis of extra-large-pore zeolites in terms of the synthesis mechanism, the directing effect of the organic structure directing agent (OSDA), the framework atoms, and the gel concentration. Extra-large-pore zeolites, including the recently discovered chiral mesoporous ITQ-37, are described and their catalytic and adsorption properties discussed. Finally, strategies are presented for the preparation of extra-large-pore zeolites with different pore topologies that can fulfill pre-established catalytic and adsorption targets.

Extra‐Large‐Pore Zeolites: Bridging the Gap between Micro and Mesoporous Structures

Composites of micro- and mesoporous materials: simultaneous syntheses of MFI/MCM-41 like phases by a mixed template approach

As-prepared, calcined and catalytically tested MCM-41 materials have been comprehensively characterised by N2 adsorption/desorption at 77 K, 1H, 27Al and 29Si MAS NMR as well as by temperature-programmed ammonia desorption (TPAD) with in situ FTIR. 29Si MAS NMR spectra of MCM-41 closely resemble those of amorphous silica, suggesting a broad range of Si—O—Si bond angles in this material. The obtained results from 1H MAS NMR and a combination of FTIR and TPAD investigations indicate that the washed, template-free MCM-41 and its protonic form behave like a solid-state acid with a broad acid strength distribution. With regard to the presence of bridging hydroxy groups in the investigated MCM-41 materials, the findings of these two methods are not consistent. Therefore, it is assumed that the broad absorption between 3650 and 3400 cm–1 in the FTIR spectra is connected with hydrogen-bonded vicinal silanol pairs. A signal in the 27Al MAS NMR spectra at 40 ppm is identified as a separate resonance, assigned preferentially to an isolated extranetwork tetrahedral aluminium species, whereby the assignment to a pentahedrally coordinated network aluminium species is also considered. When calcined, these species are reinserted into network positions. Subsequent catalytic testing leads to partial recovery of the former resonance. The results of the catalytic testing imply that the weak Bronsted acid sites interact with neighbouring coordinatively unsaturated aluminium species and that synergistically stronger acid sites form.

Textural, structural and acid properties of a catalytically active mesoporous aluminosilicate MCM-41

The catalytic properties of extra-large pore aluminosilicate MCM-41 and a silica-containingVPI-5 were investigated by MAT ( M icro A ctivity T est) using n-hexadecane as a model feed and were then compared with the results obtained from a commercial FCC catalyst (FCC: F luid C atalytic C racking) It could be demonstrated that, by optimizing structural and chemical properties, the new mesoporous crystalline MCM-41 and related materials are suitable as active components in cracking catalysts for “deeper” cracking of high boilding hydrocarbons

Catalytic properties of mesoporous crystalline MCM-41 and related materials forhydrocarbon cracking

mesoporous MCM-41 materials — Effect of acidity and porosity on catalytic properties

Characterisation studies on the new microporous aluminium-containing ETS-10 molecular sieve used for processing larger molecules

The catalytic properties of extra-large pore aluminosilicate MCM-41, silicon containing VPI-5 and aluminium containing ETS-10 were investigated by MAT (Micro Activity Test) using n-hexadecane and 1,3,5-triisopropylbenzene as the model feeds and were then compared with the results obtained from Y zeolite in the H-form and a commercial FCC (Fluid Catalytic Cracking) catalyst. It could be demonstrated that not only the acidic properties of the investigated materials, but also the accessibility to the internal active sites of the investigated materials have a significant influence on activity and selectivity. It can be assumed that, by optimising structural and chemical properties, the mesoporously organised MCM-41 and related materials are suitable as active components in cracking catalysts for “deeper” cracking of high boiling hydrocarbons.

A. Liepold

Papers

Textural, structural and acid properties of a catalytically active mesoporous aluminosilicate MCM-41

Catalytic properties of mesoporous crystalline MCM-41 and related materials forhydrocarbon cracking

mesoporous MCM-41 materials — Effect of acidity and porosity on catalytic properties

Characterisation studies on the new microporous aluminium-containing ETS-10 molecular sieve used for processing larger molecules

Impact of accessibility and acidity on novel molecular sieves for catalytic cracking of hydrocarbons