Use of amphiphilic triblock copolymers to direct the organization of polymerizing silica species has resulted in the preparation of well-ordered hexagonal mesoporous silica structures (SBA-15) with uniform pore sizes up to approximately 300 angstroms. The SBA-15 materials are synthesized in acidic media to produce highly ordered, two-dimensional hexagonal (space group p6mm) silica-block copolymer mesophases. Calcination at 500°C gives porous structures with unusually large interlattice d spacings of 74.5 to 320 angstroms between the (100) planes, pore sizes from 46 to 300 angstroms, pore volume fractions up to 0.85, and silica wall thicknesses of 31 to 64 angstroms. SBA-15 can be readily prepared over a wide range of uniform pore sizes and pore wall thicknesses at low temperature (35° to 80°C), using a variety of poly(alkylene oxide) triblock copolymers and by the addition of cosolvent organic molecules. The block copolymer species can be recovered for reuse by solvent extraction with ethanol or removed by heating at 140°C for 3 hours, in both cases, yielding a product that is thermally stable in boiling water.

Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores

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

Hollow micro-/nanostructures are of great interest in many current and emerging areas of technology. Perhaps the best-known example of the former is the use of fly-ash hollow particles generated from coal power plants as partial replacement for Portland cement, to produce concrete with enhanced strength and durability. This review is devoted to the progress made in the last decade in synthesis and applications of hollow micro-/nanostructures. We present a comprehensive overview of synthetic strategies for hollow structures. These strategies are broadly categorized into four themes, which include well-established approaches, such as conventional hard-templating and soft-templating methods, as well as newly emerging methods based on sacrificial templating and template-free synthesis. Success in each has inspired multiple variations that continue to drive the rapid evolution of the field. The Review therefore focuses on the fundamentals of each process, pointing out advantages and disadvantages where appropriate. Strategies for generating more complex hollow structures, such as rattle-type and nonspherical hollow structures, are also discussed. Applications of hollow structures in lithium batteries, catalysis and sensing, and biomedical applications are reviewed.

Hollow Micro-/Nanostructures: Synthesis and Applications**

Nanostructured materials: basic concepts and microstructure☆

ion. The oxidative addition mechanism was originally proposed22i because of the lack of a strong rate dependence on polar factors and on the acidity of the medium. Later, however, the electrophilic substitution mechanism also was proposed. Recently, the oxidative addition mechanism was confirmed by investigations into the decomposition and protonolysis of alkylplatinum complexes, which are the reverse of alkane activation. There are two routes which operate in the decomposition of the dimethylplatinum(IV) complex Cs2Pt(CH3)2Cl4. The first route leads to chloride-induced reductive elimination and produces methyl chloride and methane. The second route leads to the formation of ethane. There is strong kinetic evidence that the ethane is produced by the decomposition of an ethylhydridoplatinum(IV) complex formed from the initial dimethylplatinum(IV) complex. In D2O-DCl, the ethane which is formed contains several D atoms and has practically the same multiple exchange parameter and distribution as does an ethane which has undergone platinum(II)-catalyzed H-D exchange with D2O. Moreover, ethyl chloride is formed competitively with H-D exchange in the presence of platinum(IV). From the principle of microscopic reversibility it follows that the same ethylhydridoplatinum(IV) complex is the intermediate in the reaction of ethane with platinum(II). Important results were obtained by Labinger and Bercaw62c in the investigation of the protonolysis mechanism of several alkylplatinum(II) complexes at low temperatures. These reactions are important because they could model the microscopic reverse of C-H activation by platinum(II) complexes. Alkylhydridoplatinum(IV) complexes were observed as intermediates in certain cases, such as when the complex (tmeda)Pt(CH2Ph)Cl or (tmeda)PtMe2 (tmeda ) N,N,N′,N′-tetramethylenediamine) was treated with HCl in CD2Cl2 or CD3OD, respectively. In some cases H-D exchange took place between the methyl groups on platinum and the, CD3OD prior to methane loss. On the basis of the kinetic results, a common mechanism was proposed to operate in all the reactions: (1) protonation of Pt(II) to generate an alkylhydridoplatinum(IV) intermediate, (2) dissociation of solvent or chloride to generate a cationic, fivecoordinate platinum(IV) species, (3) reductive C-H bond formation, producing a platinum(II) alkane σ-complex, and (4) loss of the alkane either through an associative or dissociative substitution pathway. These results implicate the presence of both alkane σ-complexes and alkylhydridoplatinum(IV) complexes as intermediates in the Pt(II)-induced C-H activation reactions. Thus, the first step in the alkane activation reaction is formation of a σ-complex with the alkane, which then undergoes oxidative addition to produce an alkylhydrido complex. Reversible interconversion of these intermediates, together with reversible deprotonation of the alkylhydridoplatinum(IV) complexes, leads to multiple H-D exchange

Activation of c-h bonds by metal complexes

A neutral templating route for preparing mesoporous molecular sieves is demonstrated based on hydrogen-bonding interactions and self-assembly between neutral primary amine micelles (S degrees ) and neutral inorganic precursors (l degrees ). The S degrees l degrees templating pathway produces ordered mesoporous materials with thicker framework walls, smaller x-ray scattering domain sizes, and substantially improved textural mesoporosities in comparison with M41S materials templated by quaternary ammonium cations of equivalent chain length. This synthetic strategy also allows for the facile, environmentally benign recovery of the cost-intensive template by simple solvent extraction methods. The S degrees 1 degrees templating route provides for the synthesis of other oxide mesostructures (such as aluminas) that may be less readily accessible by electrostatic templating pathways.

http://science.sciencemag.org/content/sci/267/5199/865.full.pdf

A neutral templating route to mesoporous molecular sieves.

Titanium silicalite is an effective molecular-sieve catalyst for the selective oxidation of alkanes, the hydroxylation of phenol and the epoxidation of alkenes in the presence of H2O2 (refs 1-3). The range of organic compounds that can be oxidized is greatly limited, however, by the relatively small pore size (about 0.6 nm) of the host framework. Large-pore (mesoporous) silica-based molecular sieves have been prepared recently by Kresge et al. and Kuroda et al.; the former used a templating approach in which the formation of an inorganic mesoporous structure is assisted by self-organization of surfactants, and the latter involved topochemical rearrangement of a layered silica precursor. Here we describe the use of the templating approach to synthesize mesoporous silica-based molecular sieves partly substituted with titanium--large-pore analogues of titanium silicalite. We find that these materials show selective catalytic activity towards the oxidation of 2,6-di-tert-butyl phenol to the corresponding quinone and the conversion of benzene to phenol.

Titanium-containing mesoporous molecular sieves for catalytic oxidation of aromatic compounds

A series of mesoporous MCM-41 and HMS silica molecular sieves have been prepared by electrostatic and neutral assembly pathways, respectively, and their properties have been compared by a variety of physical techniques. Direct S+I- charge matching between cationic quaternary ammonium ion surfactants (S+) and the anionic silicate precursors (I-) affords long-range hexagonal structures under hydrothermal synthesis conditions (100 °C), but the long-range order is greatly reduced when the synthesis is conducted at ambient temperature. Conversely, owing to weaker assembly forces, counterion-mediated S+X-I+ and neutral S0I0 pathways (where X- is halide and S0 is a primary amine) provide calcined products with the best long-range order when the syntheses are conducted at ambient temperature. In general, MCM-41 silicas formed by electrostatic S+I- or S+X-I+ assembly exhibit greater long-range order than the HMS analogues prepared by the S0I0 assembly. However, the framework-confined pore structures, though depend...

Mesoporous silica molecular sieves prepared by ionic and neutral surfactant templating : A comparison of physical properties

A biomimetic templating approach to the synthesis of lamellar silicas is demonstrated. The procedure is based on the hydrolysis and cross-linking of a neutral silicon alkoxide precursor in the interlayered regions of multilamellar vesicles formed from a neutral diamine bola-amphiphile. Unlike earlier surfactant-templating approaches, this method produces porous lamellar silicas (designated MSU-V) with vesicular particle morphology, exceptional thermal stability, a high degree of framework cross-linking, unusually high specific surface area and pore volume, and sorption properties that are typical of pillared lamellar materials. This approach circumvents the need for a separate pillaring step in building porosity into a lamellar host structure and offers new opportunities for the direct fabrication of adsorbents, catalysts, and nanoscale devices.

https://science.sciencemag.org/content/sci/271/5253/1267.full.pdf

Biomimetic Templating of Porous Lamellar Silicas by Vesicular Surfactant Assemblies

A family of silica molecular sieves with lamellar frameworks and hierarchical structure (denoted MSU-V) was assembled from homogeneous solutions of neutral H2N(CH2)nNH2 bolaamphiphiles (n = 12−22) as the structure directors and tetraethylorthosilicate as the inorganic precursor Optimal lamellar order was observed for four as-synthesized and calcined (550 °C) mesostructures when they were assembled at the following reaction temperatures (T, °C) and surfactant/silica ratios (R) of T = 25 °C, R = 026 (C12); T = 45 °C, R = 020 (C16); T = 55 °C, R = 015 (C18); T = 55 °C, R = 011 (C22) MSU-V silica assembled from the short C12 alkyl chain bolaamphiphile exhibited gallery-confined micropores (13 nm), but the derivatives prepared from the longer C16−C22 diamines showed gallery-confined mesopores As the alkyl chain length of the bolaamphiphile surfactant increased from C16 to C22, the size of the gallery-confined mesopores increased from 20 to 27 nm The described synthetic strategy afforded hierarchical

Peter T. Tanev

Papers

A neutral templating route to mesoporous molecular sieves.

Titanium-containing mesoporous molecular sieves for catalytic oxidation of aromatic compounds

Mesoporous silica molecular sieves prepared by ionic and neutral surfactant templating : A comparison of physical properties

Biomimetic Templating of Porous Lamellar Silicas by Vesicular Surfactant Assemblies

Assembly of Mesoporous Lamellar Silicas with Hierarchical Particle Architectures