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

Layered double hydroxides (LDHs) are a class of ionic lamellar compounds made up of positively charged brucite-like layers with an interlayer region containing charge compensating anions and solvation molecules. Delamination of LDHs is an interesting route for producing positively charged thin platelets with a thickness of a few atomic layers, which can be used as nanocomposites for polymers or as building units for making new designed organic-inorganic or inorganic-inorganic nanomaterials. The synthesis of nanosized LDH platelets can be generally classified into two approaches, bottom-up and top-down. It requires modification of the LDH interlamellar environment and then selection of an appropriate solvent system. In DDS intercalated LDHs, the aliphatic tails of the DDS- anions exhibit a high degree of interdigitation in order to maximize guest-guest dispersive interactions. Bellezza reported that the LDH colloids can also been obtained by employing a reverse microemulsion approach.

Recent advances in the synthesis and application of layered double hydroxide (LDH) nanosheets.

Single layered polysilicate kanemite (NaHSi2O5·3H2O) was allowed to react with alkyltrimethylammonium chloride solutions to form alkyltrimethylammonium–kanemite complexes. During the organic intercalation, the SiO2 layers in the complexes were condensed to form three-dimensional SiO2 networks. The calcined products of the complexes had micro pores 2–4 nm in diameter, and the surface areas were ca. 900 m2g−1. The pore size of the calcined products was altered with the variation in the alkyl-chain length of the alkyltrimethylammonium ions employed.

The preparation of alkyltrimethylammonium-kanemite complexes and their conversion to microporous materials.

The ion exchange reaction of interlayer Na+ ions of a layered polysilicate kanemite with alkyltrimetnylammonium ions, followed by calcination, gives highly ordered mesoporous materials with a hexagonal array of uniform channels.

Synthesis of highly ordered mesoporous materials from a layered polysilicate

Layered double hydroxides (LDHs) have been investigated for many years as host materials for a range of anion exchange intercalation reactions. In this role they have been used extensively as ion-exchange materials, catalysts, sorbents and halogen absorbers. More recently, there have been a tremendous number of new developments using these materials to store and deliver biologically active materials in vivo. Significant advances have been made recently on the characterisation of these materials, including structural studies and on the mechanism of intercalation using in situ techniques.

Intercalation chemistry of layered double hydroxides: recent developments and applications

Layered double hydroxides are antitypes of 2/1 clay minerals. In spite of a high surface charge density, as in micas, they react easily with various types of organic anions. Short- and long-chain anions are rapidly exchanged for the inorganic interlayer anions, and high degrees of reaction are attained. The pronounced preference of primary long-chain compounds as typical of the more highly charged clay minerals is not observed. The small equivalent area forces the alkyl chain compounds (fatty acid anions, dicarboxylates, alkyl sulfates) to point away from the interlamellar surfaces and to form monomolecular films of high regularity

Anion-exchange reactions of layered double hydroxides

Hydroxy double salts (HDS's) comprise a class of layered materials which are similar to layered double hydroxides (LDH's) and show a comparable intracrystalline reactivity. All samples described in this paper were prepared by reacting a solid oxide MeO with various solutions.

Anion-exchange reactions of hydroxy double salts

Presently, a large variety of layered materials are synthesized that are able to intercalate neutral guest molecules or to exchange inorganic and organic ions for interlayer ions. Several of these materials are also found as minerals.

Klaus Beneke

Papers

Anion-exchange reactions of layered double hydroxides

Anion-exchange reactions of hydroxy double salts

Intercalation and exchange reactions of clay minerals and non-clay layer compounds

Anionic surfactants between double metal hydroxide layers

Magadiite and H-magadiite: I. Sodium magadiite and some of its derivatives