Although gold is the subject of one of the most ancient themes of investigation in science, its renaissance now leads to an exponentially increasing number of publications, especially in the context of emerging nanoscience and nanotechnology with nanoparticles and self-assembled monolayers (SAMs). We will limit the present review to gold nanoparticles (AuNPs), also called gold colloids. AuNPs are the most stable metal nanoparticles, and they present fascinating aspects such as their assembly of multiple types involving materials science, the behavior of the individual particles, size-related electronic, magnetic and optical properties (quantum size effect), and their applications to catalysis and biology. Their promises are in these fields as well as in the bottom-up approach of nanotechnology, and they will be key materials and building block in the 21st century. Whereas the extraction of gold started in the 5th millennium B.C. near Varna (Bulgaria) and reached 10 tons per year in Egypt around 1200-1300 B.C. when the marvelous statue of Touthankamon was constructed, it is probable that “soluble” gold appeared around the 5th or 4th century B.C. in Egypt and China. In antiquity, materials were used in an ecological sense for both aesthetic and curative purposes. Colloidal gold was used to make ruby glass 293 Chem. Rev. 2004, 104, 293−346

Gold nanoparticles: assembly, supramolecular chemistry, quantum-size-related properties, and applications toward biology, catalysis, and nanotechnology.

This critical review shows the basis of photocatalytic water splitting and experimental points, and surveys heterogeneous photocatalyst materials for water splitting into H2 and O2, and H2 or O2 evolution from an aqueous solution containing a sacrificial reagent Many oxides consisting of metal cations with d0 and d10 configurations, metal (oxy)sulfide and metal (oxy)nitride photocatalysts have been reported, especially during the latest decade The fruitful photocatalyst library gives important information on factors affecting photocatalytic performances and design of new materials Photocatalytic water splitting and H2 evolution using abundant compounds as electron donors are expected to contribute to construction of a clean and simple system for solar hydrogen production, and a solution of global energy and environmental issues in the future (361 references)

Heterogeneous photocatalyst materials for water splitting

2.3. Evaluation of Photocatalytic Water Splitting 6507 2.3.1. Photocatalytic Activity 6507 2.3.2. Photocatalytic Stability 6507 3. UV-Active Photocatalysts for Water Splitting 6507 3.1. d0 Metal Oxide Photocatalyts 6507 3.1.1. Ti-, Zr-Based Oxides 6507 3.1.2. Nb-, Ta-Based Oxides 6514 3.1.3. W-, Mo-Based Oxides 6517 3.1.4. Other d0 Metal Oxides 6518 3.2. d10 Metal Oxide Photocatalyts 6518 3.3. f0 Metal Oxide Photocatalysts 6518 3.4. Nonoxide Photocatalysts 6518 4. Approaches to Modifying the Electronic Band Structure for Visible-Light Harvesting 6519

Semiconductor-based Photocatalytic Hydrogen Generation

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

3.2.3. Hydroformylation 2467 3.2.4. Dimerization 2468 3.2.5. Oxidative Cleavage and Ozonolysis 2469 3.2.6. Metathesis 2470 4. Terpenes 2472 4.1. Pinene 2472 4.1.1. Isomerization: R-Pinene 2472 4.1.2. Epoxidation of R-Pinene 2475 4.1.3. Isomerization of R-Pinene Oxide 2477 4.1.4. Hydration of R-Pinene: R-Terpineol 2478 4.1.5. Dehydroisomerization 2479 4.2. Limonene 2480 4.2.1. Isomerization 2480 4.2.2. Epoxidation: Limonene Oxide 2480 4.2.3. Isomerization of Limonene Oxide 2481 4.2.4. Dehydroisomerization of Limonene and Terpenes To Produce Cymene 2481

Chemical Routes for the Transformation of Biomass into Chemicals

A new family of hybrid mesoporous materials containing a variety of bridging organic groups inside the pore walls is reported. A short review about the previous studies on the synthesis of organic-bridged mesoporous materials along with our recent research works on the formation of crystal-like ordered structure in the pore walls of organic-bridged mesoporous materials as well as the functionalization of ordered pore-walls of mesoporous benzene-silica with sulfuric acid groups is summarized.

A new family of organic-bridged mesoporous materials

Two different microscopic phases have been observed via inelastic neutron scattering for superfluid helium confined within highly monodisperse, smooth, and unidimensional silica pores. When the helium forms a thin film on the pore walls, it supports a dramatically modified phonon-roton spectrum as well as a 2D surface roton. The energies of these modified phonon-roton modes are consistent with predictions for a dilute, low-density film, while the energy of the 2D surface roton corresponds to that of a dense film. The relatively smooth and weak surface potential of the substrate permits the formation of a film with large dilute regions and only small compressed regions. When the pores are saturated with liquid, the modified phonon-roton spectrum disappears, and bulk-like modes coexist with the 2D surface roton. Presumably, bulk-like liquid occupies the core volume of the pores and high density liquid layers are present at the liquid-solid interface. These findings clearly connect the nature of the excitations to the local density of the liquid.

Phases of Superfluid Helium in Smooth Cylindrical Pores

層状ケイ酸塩のカネマイトからその単位シートを折り曲げることによりメソポア結晶が得られることを著老らは示した.ポリケイ酸の構造,それらのインターカレーショソ反応,シリケート層間の縮合反応,シート折り曲げによるメソポア材料(FSM)の生成機構,およびそれらの応用の可能性についてまとめた.ニケイ酸ナトリウム(Na2Si2O5)やカネマイト(NaHSi2O5)はSiO4-四面体イオンと層間陽イオンとで構成されている.この陽イオンを有機陽イオンで交換することによりポリケイ酸と有機イオソとの複合体が得られるiホストにカネマイトを用いた場合,単位シート間の縮合反応がイオン交換反応と同時に観測された.この有機陽イオンを焼成除去することによりメソポア材料が得られた.このイオン交換をpH=12で行うと,Sio4一四面体シート問の縮合は起こらず,シートの折り曲げのみが進行した.その後,pHを8.5に調整することによりシート間の縮合が進み六方対称を持っポリケイ酸/有機複合体が得られた.これを550℃ で焼成することにより,均一な孔径の細孔が規則的に配列した結晶が得られた.著者らはこの生成機構をシート折り曲げ機構と呼び,合成された材料をFSM(Folded Sheets Mechanism, Folded Sheets Mesoporous Materials)と呼んでいる.管状の形の有機陽イオンでイオン交換したり,上記のイオン交換の際にアルコールを添加することにより層状構造の複合体が得られることも確認された.このようにして合成されたメソポア材料(FSM)は吸着剤,触媒,あるいは金属や半導体のナノクラスター合成のホスト材としてなどの応用が期待されている.

Mesoporous Materials with Uniform Pore Size; Synthesis and Their Applications.

Enhanced Photoluminescence of Mesostructured Organosilica Films with a High Density of Fluorescent Chromophores

3-Mercaptopropylpolysilsesquioxanes (poly-MTS) were synthesized by the stepwise hydrolytic polycondensation of 3-mercaptopropyl-(trimethoxy)silane (MTS) in the presence of hydrochloric acid as a catalyst in a nitrogen stream. Poly-MTS was mainly composed of the silsesquioxane structure with an average formula (HS(CH2)3Si(O3/2))n. The content of silsesquioxane structure in the polymer increased with increasing water content. A transparent free-standing film was prepared by heating a tetrahydrofuran solution of poly-MTS for 14 d at 80°C.

Shinji Inagaki

Papers

A new family of organic-bridged mesoporous materials

Phases of Superfluid Helium in Smooth Cylindrical Pores

Mesoporous Materials with Uniform Pore Size; Synthesis and Their Applications.

Enhanced Photoluminescence of Mesostructured Organosilica Films with a High Density of Fluorescent Chromophores

Preparation of free-standing films from 3-mercaptopropylpolysilsesquioxane