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.

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

Although homogeneous gold catalysis was known previously, an exponential growth was only induced 12 years ago. The key findings which induce that rise of the field are discussed. This includes early reactions of allenes and furanynes and intermediates of these conversions as well as hydroarylation reactions. Other substrate types addressed are alkynyl epoxides and N-propargyl carboxamides. Important vinylgold intermediates, the transmetalation from gold to other transition metals, the development of new ligands for gold catalysis, and significant contributions from computational chemistry are other crucial points for the field highlighted here.

Gold-Catalyzed Organic Reactions

Interest in catalysis by metal nanoparticles (NPs) is increasing dramatically, as reflected by the large number of publications in the last five years. This field, "semi-heterogeneous catalysis", is at the frontier between homogeneous and heterogeneous catalysis, and progress has been made in the efficiency and selectivity of reactions and recovery and recyclability of the catalytic materials. Usually NP catalysts are prepared from a metal salt, a reducing agent, and a stabilizer and are supported on an oxide, charcoal, or a zeolite. Besides the polymers and oxides that used to be employed as standard, innovative stabilizers, media, and supports have appeared, such as dendrimers, specific ligands, ionic liquids, surfactants, membranes, carbon nanotubes, and a variety of oxides. Ligand-free procedures have provided remarkable results with extremely low metal loading. The Review presents the recent developments and the use of NP catalysis in organic synthesis, for example, in hydrogenation and C--C coupling reactions, and the heterogeneous oxidation of CO on gold NPs.

Nanoparticles as Recyclable Catalysts: The Frontier between Homogeneous and Heterogeneous Catalysis

ion from a primary OH group of glyc-erol. 223,231 A similar mechanism was proposed manyyears ago for alcohol oxidation on Pt/C, involving asecond step, the transfer of a hydride ion to the Ptsurface (Scheme 11). 8,87,237 We consider it more feasible that the rate-deter-mining step is the cleavage of the C-H bond at theR-carbon atom. A similar mechanism is now generallyaccepted for Au electrodes (Scheme 12). 238 Despite thestructural differences between Au nanoparticles andan extended Au electrode surface, there are alsosimilarities, such as the critical role of aqueousalkaline medium and the absence of deactivation dueto decomposition products (CO and C x H y frag-ments). 239,240 An important question is the nature of active siteson Au nanoparticles. Electrooxidation of ethanol onAu nanoparticles supported on glassy carbon re-quired the partial coverage of Au surface by oxides. 241 Another analogy might be the model proposed for COoxidation. 219,242,243 According to this suggestion, theactive site consists of an ensemble of metallic Auatoms and a cationic Au

Oxidation of Alcohols with Molecular Oxygen on Solid Catalysts

Graphene quantum dots for cancer targeted drug delivery.

Hydrogenation of α,β-unsaturated aldehydes over PtSn/Nylon

Coprecipitated Au/Fe2O3 catalysts used for low-temperature catalytic oxidation of carbon monoxide have been studied by FT-IR spectroscopy of adsorbed CO. The FT-IR results have shown that after preparation and exposure to a CO/O2 mixture gold is present on the surface mainly as Au1+ and Au0 species. It has been found that in the CO oxidation Au1+ is more active and less stable than Au0.

FT-IR study of Au/Fe2O3 catalysts for CO oxidation at low temperature

This paper reports a study on the influence of calcination pretreatments on the catalytic behaviour of the Au/iron oxide system towards the combustion of some representative volatile organic compounds (2-propanol, ethanol, methanol, acetone and toluene). The catalytic activity of Au/Fe 2 O 3 samples towards the total oxidation to CO 2 has been found to be strongly dependent on the catalyst pretreatment, decreasing on increasing the calcination temperature. On the basis of characterisation data (XPS, FT-IR, XRD, BET surface area) it has been proposed that the catalytic behaviour is related to the gold state and/or the iron oxide phase. It appears plausible to suggest that the gold oxidation state and/or the particle size play a key role in the catalytic combustion of volatile organic compounds.

Influence of catalyst pretreatments on volatile organic compounds oxidation over gold/iron oxide

This paper reports the effect of noble metal addition (Ru, Pd) to supported Ni catalysts towards the reaction of CO2 reforming of methane. On the basis of FT-IR spectra of adsorbed CO, H2 chemisorption and TPR measurements it has been proposed that the different behaviour of the Ni-based bimetallic catalysts can be related to different metal–metal interactions occurring on the catalysts. In particular, the strong improvement in the activity and stability observed in the case of ex-nitrate Ni–Ru catalysts has been attributed to an enrichment of the catalyst surface in nickel due to the formation of Ni–Ru clusters with the surface mainly covered by Ni. This leads to an increase in the metallic dispersion of Ni and favours the formation of more reactive intermediate carbonaceous species.

Signorino Galvagno

Papers

Graphene quantum dots for cancer targeted drug delivery.

Hydrogenation of α,β-unsaturated aldehydes over PtSn/Nylon

FT-IR study of Au/Fe2O3 catalysts for CO oxidation at low temperature

Influence of catalyst pretreatments on volatile organic compounds oxidation over gold/iron oxide

CO2 reforming of methane over Ni–Ru and Ni–Pd bimetallic catalysts