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By Susumu Tsubota

Three types of reference gold catalysts, i.e., 3wt%Au/TiO2 (Au-Ti: Type A), and 0.3wt%Au/Fe2O3 on alumina beads (AUS: Type B), and 5wt%Au/Fe2O3 (Au-Fe: Type C), were produced in a test plant scale by Sud-Chemie Catalysts Japan, INC. under the licensing of AIST. To evaluate the validity of the preparation methods and conditions used for the reference samples, elemental analyses by ICP, particle size measurements by TEM, and catalytic activity measurements for the oxidation of CO and H2 over these catalysts were made. Gold catalysts can be prepared in a large scale of ca 400g for the Au-Ti and Au-Fe catalysts, 5 kg for the AUS catalyst with good reproducibility. It was confirmed that they were available for useful as the reference gold catalysts of World Gold Council.

Oct 1, 2003

By Laurence D. Burke

The electrocatalytic behaviour of gold in aqueous media is surprisingly complex and a novel view of gold electrode surfaces is proposed to explain the observed electrochemical responses. The metal surface is considered as a chemically (or redox) modified electrode, with equilibrated, low energy, surface gold atoms functioning as a relatively inert support and low coverage, high energy, protruding gold atoms (or minute clusters of same) functioning as electrocatalytic redox mediators. The protruding atoms are viewed as surface active sites and the complex electrocatalytic behaviour is attributed to the basic instability of the mediators, the diversity (and poor control) of same, and the acid/base (or hydrolysis) behaviour of the oxidized states of the mediators. It is assumed that major advances in the application of gold in the heterogeneous catalysis of gas phase reactions will be accompanied by similar advances in the use of gold in the electrocatalysis area; however, this will require considerable work of both a practical and theoretical nature.

Oct 1, 2003

By Golaleh Riahi

An original method is used to obtain stable nanoparticles of gold-based mono- and bimetallic systems supported on an acidic zeolite. This approach has been applied to PtHY (1wt% Pt) and to bimetallic Pt-AuHY containing 1% of platinum to which is added the amount of gold required to give Au/Pt molar ratios of 20,40,60 and 80%. Metal clusters of Au or Pt-AuHY are formed inside the supercages of the zeolite framework by the thermal reduction of cations by the ligands (en = H2N-CH2-CH2-NH2) under inert gas flow at a temperature depending on the metal. The use of acidic zeolites favours the dispersion of the metal and the thermal stability of the particles. This stability is explained by chemical anchoring of metal clusters by the Brønsted sites of the support. Several techniques have proved that for a molar ratio of 20% metal particles of Pt-AuHY are bimetallic. The segregation of Pt and Au starts for molar ratio =?40%. The catalysts tested on the methylcyclopentane hydroconversion reaction reveal that the addition of gold to platinum leads to an increase in the activity and an improvement in the selectivity for isomerization of the skeleton (cyclohexane and benzene) to the detriment of hydrogenolysis. Similar results were obtained for the dodecane isomerisation to isododecane. These catalysts were also tested in CO, propene and propane oxidation. The activity of fresh catalysts is rather low. It increases after their pretreatment in oxygen or hydrogen atmosphere. In propene oxidation in the reaction mixture O2 ? H2, beside total oxidation of propene to CO2, also propene hydrogenation was observed, particularly at low temperatures. The presence of Au enhances the hydrogenation properties: high selectivities (> 90%) to propane and high propane yields on PtAu HY are observed up to ~150oC, whereas for Pt HY catalyst the selectivity and yield to C3H8 decreases rapidly with the temperature beginning from ~100oC.

Oct 1, 2003

By Masami Nakamoto

Controlled thermolysis of gold(I) thiolate complex, [C14H29(CH3)3N][Au(SC12H25)2], at 180 °C for 5 h under an N2 atmosphere produces novel gold nanoparticles passivated by alkyl groups derived from the precursor complex, the TEM photograph of which shows spherical particles with average diameter 26 nm. Since Brust et al. reported the two-phase reduction of AuCl4 - by NaBH4 to afford monodispersed gold nanoparticles passivated by alkanethiolate ligands (1), plenty of preparative investigations on gold nanoparticles (2,3) and its surface modification (3,4) have appeared, because of their potential applications in microelectronics (5). However, those preparative methods generally involve the reduction of AuCl4 - by reducing agent NaBH4 in the presence of suitable organic stabilizers such as alkanethiol (1-4), phosphane (5), quarternary ammonium salts (6), surfactants (7) or polymers (8). On the other hand, O?Brien et al. recently reported the preparation of organically capped gold nanoparticles at 190 °C, where tri-n-octylphosphine oxide and/or n-octadecylamine are used both as a reaction medium and as a passivating ligand (6), but this procedure also needs NaBH4 as reducing agent. Our strategy of novel preparative method of gold nanoparticles is the combination of reductive elimination of thiolate ligands and simultaneous attachment of organic moiety on the growing nuclei. Gold(I) thiolate complexes with ammonium cations were useful for our preparative method. We now report the controlled thermolysis of gold(I) thiolate complexes, [R(CH3)3N][Au(SC12H25)2] and [R(CH3)3N][Au(SC6H4-p-R?)2] (R= C14H29, C12H25; R?= C8H17, CH3), under an N2 atmosphere, where the powder of gold(I) thiolate complexes completely melts to afford the precursor liquid and then the liquid gradually decomposes. In spite of no use of reducing agent and solvent, reduction reaction is thermochemically induced to afford novel gold nanoparticles passivated by alkyl groups rather than by alkanethiolate ligands. Figure 1a shows a typical transmission electron microscopy (TEM) image of gold nanoparticles prepared by thermolysis of [C14H29(CH3)3N][Au(SC12H25)2] at 180 °C for 5 h, indicating a controlled growth of spherical gold nanoparticles. As shown in Fig. 1b, these spherical gold nanoparticles display the size distribution ranging from 5 to 50 nm. Although the particle size is larger than that of thiol-derivatized gold nanoparticles (less than 5 nm) prepared by NaBH4 reduction (1-3), the aggregation of gold nuclei is smoothly regulated and the growth of core gold is limited to be 26 nm in average diameter in spite of thermal procedure.

Oct 1, 2003

By Toshiharu Teranishi

When we apply the Au nanoparticle superlattices to the future nanooptical and nanoelectronic devices, the control of not only the particle size but also the interparticle spacing and symmetry of superlattice are the essential problems to be overcome. First, we developed a novel synthetic procedure to precisely control the particle size of alkanethiol-protected Au nanoparticles in the range from 1.5 to 9.7 nm by the heat-treatment of the small Au nanoparticles in the solid state. Absorption and nonlinear optical properties of alkanethiol-protected Au nanoparticle superlattices were then elucidated. On the other hand, the hexagonal close-packed (hcp) 2D superlattices of small Au nanoparticles with the interparticle spacings from 1.9 to 3.6 nm were successfully prepared by using newly-synthesized ligand for single electron tunneling devices. Finally, various symmetric superlattices, such as chain (2-fold), quasi-honeycomb (3-fold), square (4-fold), etc., of Au nanoparticles could be produced by making use of interligand interactions or some templates.

Oct 1, 2003

By Fernando Canales

In the last decade a great dealt of attention has been paid to the chemistry of polynuclear gold derivatives with a central heteroatom, not only from the experimental and structural but also from the theoretical standpoint (1). Interesting hypercoordinated species of the type [C(AuPR3)5]+, [C(AuPR3)6]2+, [N(AuPR3)5]2+, [P(AuPR3)5]2+ and [P(AuPR3)6]3+ have been described (2), apart from other complexes with more conventional stoichiometry, and all have in common the presence of gold-gold interactions of ca. 3 Å. Usually, the chemistry of the first row elements of the p-block is known to follow classical rules of bonding, and only in cases of extreme electron-deficiency has the traditional electron count to be reconsidered to account for special types of molecular or solid state structures. Many of these heteroatomcentered complexes are electron-deficient and the gold-gold interactions provide a significant contribution to their stability. The attraction between these closed-shell systems has recently captured the attention in inorganic and organometallic chemistry (1). P. Pyykkö has summarized the available theoretical and experimental evidence of intra- and inter-molecular interactions between heavy metal atoms, such as Au(I) (3). In general, when heavy metals are involved in such interaction, the closed-shell attractions are of metallophilic or van der Waals type, as has been found for d8, d10 coinage-metals, and d10s2 centers. Experimental evidence for the aurophilic Au(I)???Au(I) attraction is available from crystallography, NMR and Raman spectroscopies, and optical spectroscopic measurements of the interaction strength (4). It is manifested in molecular conformations with relatively close Au???Au interactions of ca. 3 Å, whose strength has been estimated at ca. 25-50 kJ/mol (5). These attractions are weaker than most covalent or ionic bonds, but stronger than other van der Waals bonds and comparable in strength to typical hydrogen bonds. The phenomenon cannot be satisfactorily explained by classical theories such as hybridization (3). From a theoretical point of view, the attractions close to equilibrium distances are caused by dispersive interactions together with relativistic effects (6). The attractive contributions are dominated by pair-excitations from the heavy metal, such as gold, strengthened by relativistic effects. In all the cases where there are inter- or intramolecular metal-metal attractions, the correlation effects are essential; if they are omitted, at the Hartree-Fock (HF) level, repulsive interactions are obtained (6). Hence, it is necessary to use at least second-order Møller-Plesset level (MP2) methods for the dispersive forces, which are included in the electronic correlation effects (7).

Oct 1, 2003

By Elma van der Lingen

Gold is considered the most inert of all metallic elements, but the metal can show catalytic activity when prepared by specific techniques. Preparation techniques being used to prepare gold catalysts systems mainly involve precipitation methods incorporating gold compounds or complexes. This paper introduces a totally different method for the preparation of gold-based heterogeneous catalysts that can be used for oxidation and reduction reactions, as well as electrocatalysts. The method involves alloying of gold with a less noble metal, such as aluminium, to form a gold-containing intermetallic precursor. AuAl2 was produced by melting gold and aluminium together in a vacuum arc furnace under a protective atmosphere. The aluminium is then dissolved from the AuAl2 precursor by means of NaOH to produce a highly porous gold structure. The paper also reports on a method of incorporating transition metal oxide(s) with the porous gold to form an active heterogeneous catalyst. Promoter elements can also be melted with AuAl2 to improve catalytic activity. Alloying has the advantage that the promoter element can be in contact on atomic level with the gold. In-situ xray photoelectron spectroscopy (XPS) studies have also been done on the porous gold catalysts to further clarify the CO oxidation mechanism on gold-based catalysts.

Oct 1, 2003

By Michael Bowker

Au/TiO2 catalysts were prepared by incipient wetness impregnation and tested for the room temperature photocatalytic reforming of methanol in aqueous solution. These catalysts proved to be more active, on a molar basis, than Pd/TiO2. The dependence on loading of gold was different from that of palladium, showing a double maximum in yield at 0.1 and 2 wt. % with low rate below 0.01% and above 10%. A model is proposed for the reaction involving band gap excitation of titania electrons which are used to oxidise the methanol via adsorbed CO. With palladium, photoreforming of CO and water can be achieved, but this is much less effective on gold, presumably due to the much weaker bonding of CO on Au.

Oct 1, 2003

By Peter J. Barnard

Mitochondria play a key role in the regulation of apoptosis (cell death) and in diseases characterised by abnormal apoptotic responses such as cancer. Mitochondrial membrane permeabilisation (MMP), regulated by the mitochondrial permeability transition pore complex, is widely accepted as being central to the process of cell death. As a result there has been considerable recent interest in targeting mitochondrial cell death pathways in the development of new chemotherapeutic agents.(1) There is potential to overcome the two overriding problems in cancer chemotherapy?the common occurrence of drug-resistant tumour cells and the lack of selectivity of cancer drugs in differentiating between tumour cells and normal tissues. Significantly, carcinoma cells have an elevated mitochondrial membrane potential relative to normal cells and lipophilic cations are concentrated within mitochondria in response to mitochondrial membrane potentials. There is potential for the selective targeting to tumour cells with compounds having optimal lipophilic-hydrophilic character. Research stemming from the early 1980?s points to two distinct classes of Au(I) phosphine antitumour agents where an antimitochondrial mode of action has been implicated: (i) neutral linear two-coordinate Au(I) complexes such as triethylphosphinegold(I) chloride and the tetraacetylthioglucose gold(I) phosphine complex, Auranofin; (ii) cationic tetrahedral bis-chelated Au(I) phosphine complexes related to [Au(dppe)2]+.(2) Recently it has been reported that Auranofin, at submicromolar concentrations, induces MMP observed as mitochondrial swelling and dissipation of membrane potential.(3, 4) Both events are completely inhibited by cyclosporin-A, the specific inhibitor of MMP. The permeability changes were shown to occur at concentrations associated with the selective inhibition of mitochondrial thioredoxin reductase.(3) Auranofin is a potent and specific inhibitor of this enzyme due to Au(I) binding to the active-site selenol group.(5) The redox state of mitochondrial thiols may be critical in the control of MMP.(3) In general, swelling is stimulated by thiol blocking or oxidising agents and is prevented by thiol reducing agents.(1) Mitochondrial thioredoxin reductase may play an import role in the redox control of the permeability of mitochondrial membranes.(3) Our interest is in investigating the antitumour potential of Au(I) phosphine compounds using a number of different approaches. In recent work we have evaluated a series of hydrophilic analogs of [Au(dppe)2]+ containing pyridylphosphine ligands which have demonstrated greater tumour selectivity than the parent compound. To investigate the possible antimitochondrial mode of action we are studying the effect of [Au(dppe)2]+ and related compounds on isolated rat liver mitochondria. To assess whether the lipophiliccationic nature of the compounds determines the antitumour activity, we have synthesized a series of novel Au(I) complexes based on heterocyclic carbene rather than phosphine ligands. The similar chemistry and structural features of the two classes of complexes allow us to assess whether the phosphine ligands are essential for the antitumour properties.

Oct 1, 2003

By Ronald L. Bruening

IBC has developed a cost effective MRT process for the selective extraction and recovery of gold, copper, and a mixture of other base metals from mine leach cyanide solutions. This is a two-stage system in which the gold is first recovered selectively as a high purity salt. The copper is then recovered separately as a sulfate salt. The other base metals are then collected as a cyano anion concentrate. Three different SuperLig® materials are used. The first stage can be used alone on gold leach solutions where copper and other base metals are not a problem. The two or three stage system is used when the base metals build up in the leach solution, resulting in increased costs. The cyanide or cyanide/cyano anion concentrate can be recycled back to the leach solution until the build-up of other salts, etc. becomes too high, or this too can be controlled with a percentage bleed stream.

Oct 1, 2003

By K. Wongpreedee

Recovery and recrystallization of Au wire can degrade strength and alter conductivity properties during exposure to elevated temperature. Au Deformation Processed Metal Metal Composites (Au DMMC's) are being developed for electronic applications requiring high conductivity and high strength. This paper discusses the relationships between microstructure, strength, and resistivity of Au DMMC's. It also presents the results of a recent study on the elevated temperature stability of Au DMMC's of several compositions. Au-7 vol %Ag, Au-14 vol %Ag, and Au-vol 7%Pt DMMC samples were prepared by a powder metallurgy technique. All specimens were processed into wire by extrusion, swaging, and drawing. The smallest final diameter of these wires was 120 ?m. Thermal stability was analyzed by electrical resistivity measurements to determine the relation between transformation rates and time at elevated temperature. The extensive deformation used to produce these composites reshaped the initially equi-axed powder into filaments that are 30 to 100 nm in diameter and 16 to 180 mm in length. The small filament diameter confers high strength on the composite. The high conductivity can be explained by electrons flowing parallel to the filamentary microstructure aligned with the wire axis. Using the Avrami and Arrhenius equation relationships, it is possible to predict the times and temperatures needed to achieve various degrees of homogenization. The Au DMMC's were found to have good thermal stability compared to conventional coldworked Au interconnection wires. Although these composites will revert to solid solutions if exposed to high temperatures for prolonged time periods, their relative stability is sufficient to allow them to maintain their twophase microstructure during the anticipated lifetime temperature profiles of many products.

Oct 1, 2003

By Mari Yamamoto

Controlled thermolysis of gold(I) complex, [Au(C13H27COO)(PPh3)], at 180 °C for 5 h under an N2 atmosphere affords the new type of monodispersed spherical gold nanoparticles capped by myristate and a small amount of PPh3 ligands (average diameter 23±1.5 nm), in spite of no use of solvent, reducing agent and stabilizer. Much attention has been paid to the preparation and structure determination of transition metal nanoparticles, because of their widespread use in technological applications.1 In general, the chemical reduction of metal salts and organometallic complexes2 by the use of reducing agent is carried out to prepare gold nanoparticles. In some cases, a large amount of solvent and stabilizers such as surfactants,3 polymers4 and ligands5 are used to prevent agglomeration of particles and control the particle size. For instance, Brust et al. reported a two-phase reduction of AuCl4 - by NaBH4 in the presence of dodecanethiol as stabilizer to prepare gold nanoparticles.6 On the other hand, O?Brien et al. recently reported an one-phase preparation of gold nanoparticles by the reduction of AuCl4 - by NaBH4 in the mixture of tri-n-octylphosphine oxide and octadecylamine which act as both solvent and stabilizer, but this procedure also needs reducing agent.7

Oct 1, 2003

By Hua-Zhong Yu

Gold is one of the most widely used substrate materials for self-assembly. Self-assembled monolayers (SAMs) prepared from alkanethiols and their derivatives on gold are the most reliable and well-studied systems to date, which have attracted much attention because of interest in two-dimensional molecular assemblies, and of their potential applications in molecular devices, sensors, and functionalized interfaces. Gold electrodes are also very important in microelectronics and electroanalytical chemistry. This work reports the characterization of a new type of gold substrates for self-assembly. The gold substrates are constructed from recordable compact disks (R-CDs) with simple and straightforward wet-chemical treatment, and can be made at desired sizes and shapes that satisfy different experimental needs. In particular, an easy, inexpensive, and reproducible method to prepare self-assembled monolayers (SAMs) on CD-R gold substrates after removing the protective polymer films with concentrated nitric acid was described.

Oct 1, 2003

By Renaud Cousin

Supported gold catalysts were prepared by Direct Anionic Exchange on an alumina support and tested during the reaction of CO oxidation and of saturated and unsaturated hydrocarbons (C1 to C3). The catalysts showed high activies over a range of concentrations and temperatures compatible with an application to automotive exhaust cleaning. Furthermore, a complete resistance to thermal ageing at 600°C in the absence or presence of water was observed due to the obtention of strongly anchored nanosized gold particles during the preparation step.

Oct 1, 2003

By Kenji Koga

In order to derive the population distribution of gold nanoparticle morphologies as a function of size, highresolution electron microscopic (HREM) observations and structural analyses were done for over 4000 particles (3-18 nm) grown by an inert gas aggregation (IGA) source using helium. To obtain structural features threedimensionally and not to skip high-contrast images, twenty photos were taken for each particle by changing tilting angle of a specimen holder in combination with the through-focus procedure. For the reliable structural determinations, HREM images and their tilting sequences were directly compared with multislice-simulation results for icosahedral, decahedral and face-centered cubic morphologies, and finally the population distribution of each morphology was obtained as a function of size. In the present sample, icosahedral particles were dominantly populated over the whole observed size range and decahedral particles with non-spherical truncated bi-pyramid shape were secondly dominant. Even though a large number of sampling has been done, few crystalline particles were observed.

Oct 1, 2003

By Heidi Fauser

The aim of the project was the development of an electroforming process for the production of medical implants out of gold. To prove the applicability of this technology, tympanostomy tubes were chosen as demonstrators. These barbell-shaped tubes are usually produced mechanically; of silicone or, for higher therapeutic demands, of metal ? gilded silver or gilded stainless steel. Gold electroforming of the tubes as an alternative manufacturing process would reduce the expenditures for the mechanical preparation and lower the corrosion susceptibility significantly. To obtain electroformed gold tubes of the desired shape, the following steps are necessary: fabrication of a negative template by drilling holes with countersinks in an insulated aluminium sheet, electroforming process, removal of the aluminium by using a sodiumhydroxide solution. For the optimisation of the shape and surface quality of the tubes respectively the simplification of the manufacturing process, various parameters were tested, e.g. aluminium quality and sheet thickness, type of insulation layer, substrate processing, hydrodynamic conditions, type of electroforming electrolyte, electrodes position, etc. The manufactured tubes were characterised in view of thickness distribution, hardness, surface roughness and purity in comparison to mechanically produced reference tubes. From the results obtained during the project it can be concluded that electroforming processes can be easily adopted for the manufacture of medical implants. The time-consuming electroforming process is by far compensated by the simultaneous production of an arbitrary number of implants.

Oct 1, 2003

By Matthew S. Hall

Gold/iron oxide catalysts have been prepared and their catalytic performance evaluated for low temperature CO oxidation. The method and temperature used to dry the sample has a significant effect on their catalytic activity. Analysis by TEM revealed the catalysts contained Au particles, although catalysts with high and low activity did not always differ in their microstructure as evidenced by TEM. Catalysts were characterised using XPS and the difference between the Au(4d) and C(1s) binding energies measured; in general the greater the difference, the higher the catalytic activity of the material.

Oct 1, 2003

By Anna Maria Venezia

Bimetallic Au-Pd catalysts supported on amorphous silica-alumina (ASA) with vary amount of alumina (0, 8, 14, 28 and 100%) were prepared by the simultaneous reduction of palladium and gold precursors by ethanol in the presence of the polyvinylpyrrolidone (PVP). X-ray diffraction and X-ray photoelectron spectroscopy analyses indicated formation of alloyed Au-Pd particles. Ammonia temperature programmed desorption measurements were performed to monitor the acid strength and the amount of acid sites on the catalysts after their reduction with 10%H2/Ar at 573 K for 1h. The effect of the support acidity on the catalytic activity was investigated in the simultaneous hydrogenation (HYD) of toluene (T) and naphthalene (NP) in the presence of dibenzothiophene (DBT). Coke formation was also determined. Under the selected conditions (P = 5.0 MPa, T = 523 K, WHSV = 41.2 h-1), all the catalysts were resistant to poisoning with 113 ppm of S (as DBT). The hydrogenation activity of toluene and the HDS activity of DBT were found to correlate with the concentration of the medium strength acid sites. The enhancement of the HYD activity and the S- tolerance was related to modifications of the electronic properties of the metal atom upon interaction with the Brönsted acid sites and upon intermetallic interaction.

Oct 1, 2003

By Gary Pattrick

A new class of spongy Au catalysts is studied for the selective catalytic reduction of NOx by propene under leanburn conditions. The spongy catalyst is an unsupported powdered Au that consists of micrometer particles (~5 microns) that have nanometer scale (~10 nm) internal skeletal structures. The effects of alloying 1 ? 50 atom % platinum group metals (M= Pt, Pd, Rh) and 5 wt% first row transition metals (M = Ti, Mn, Fe, Co) were studied. Even low additions of PGMs (1 at.%) cause significant shifts to lower temperature regions of activity and the largest shift is obtained for Rh. For Rh this is interpreted as a strong synergistic interaction between Rh and Au. Possibly related to the Rh effect, Co is the only other metal studied that lowers the temperature of NOx reduction. The other first row transition metals inhibit the reduction reaction.

Oct 1, 2003

By Jolanta Olkowska-Oetzel

Reactions of gold?phosphino complexes [(AuX)(PR3)] (X= Cl, Br, I; R = organic rest) with Se(SiMe3)2 lead to the formation of gold complexes with chalcogenide bridges. The reaction of the complex Ph3PAuCl and tBuSe(SiMe3) gives the cluster [Au5Se2(PPh3)4]Cl 1. The in situ preparation of the complex [(AuCl)2dpph] (dpph = Ph2P(CH2)6PPh2) by reaction of dpph with Me2SAuCl, and subsequent reaction with Se(SiMe3)2 leads to the formation of [(Au3Se)2(dpph)3]Cl2 2. Reactions of the gold(I) complex [(AuCl)2dpppe], (dpppe = Ph2P(CH2)5PPh2) with Se(SiMe3)2 and InCl3 in different molar ratios lead to the formation of [Au10Se4(dpppe)4]InCl5 3 and [Au4(SeInCl3)2(dpppe)2] 4. The reaction of [(AuCl)2dpph] with Te(SiMe3)2 and GaCl3 produces the isostructural cluster compound [Au4(TeGaCl3)2(dpph)2] 5. From the reaction of Se(SiMe3)2 with [(AuCl)2dppe] (dppe = Ph2P(CH2)2PPh2) and InCl3 [Au8Se4In(dppe)4](InCl4)3 6 can be isolated. The structures of 1 - 6 were determined by X?ray diffraction.

Oct 1, 2003