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By Stephen J. Roberts

Gold catalysts were prepared on co-precipitated, calcined copper oxide - zinc oxide support by an inverse deposition-precipitation method. These catalysts were characterised by X-ray diffraction (XRD) and temperature-programmed reduction (TPR) and studied for CO oxidation activity at various catalyst calcination temperatures. TPR studies of the support material exhibited a double peak and shift to lower temperatures for the reduction of Cux+ to metallic copper, as opposed to the single reduction peak for pure CuO. This phenomenon is possibly caused by an interaction with the zinc oxide. The addition of gold to the support CuOZnO led to a further shift in copper reducibility to lower temperatures. Gold present in the initial uncalcined catalyst as Au3+ was auto-reduced to Au0 under various calcination temperatures. The Au3+ reduction peak was observed to shift to lower temperatures with increasing calcination temperature. The catalytic activity was found to pass through a minimum value with respect to calcination temperature. Catalysts with both gold in entirely the 3+ or metallic oxidation state were found to exhibit high activity. Furthermore, the catalysts were found to decrease in activity with decreasing Au3+ content up to an intermediate calcination temperature, afterwhich the activity increased sharply. Possibly at higher temperatures, a stronger Au-support interaction is formed, leading to a new active site.

Oct 1, 2003

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 Edward R. T. Tiekink

Metal complexes continue to find therapeutic applications for the treatment of a wide variety of human ailments. Amongst these, gold(I) thiolates are used to treat rheutmatoid arthritis but, usually in combination with other treatment or as a last resort. New therapeutic uses of gold, both as gold(I) and gold(III), are being sought, including against cancer, the focus of the present contribution. It will be demonstrated that certain gold(I) complexes show exciting cytotoxicity profiles, rivalling those of cisplatin and standard chemotherapeutic agents. More importantly, anti-tumour activity is demonstrated in vivo, albeit in a mouse model. The presentation will give a brief overview of ?metals in medicine? with a focus on gold and will summarise some recent advances in the development of goldbased anti-tumour agents.

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 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 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 Rodolfo Zanella

Au/TiO2 catalysts were prepared by deposition-precipitation using NaOH (DPN) (~3 wt % Au) and urea (DPU) (~8 wt % Au), and calcined at various temperatures between 100 and 400 °C. They were characterized by UV-Visible, XANES, EXAFS and TEM. Their activity were tested in the reaction of CO oxidation at 5°C. After preparation, the gold species are in the oxidic state III. They begin to transform into metallic gold under air at ~100 °C for DPN and ~150 °C for DPU. At 200 °C, all the gold is metallic for the two preparation methods. The particle size increases from 1.5 to 3.5 nm with the calcination temperature. The catalytic activity for CO oxidation increases with the percentage of metallic gold, and it is maximum at 200°C for both types of samples. The activities (per mole of Au) are the same for the two types of catalysts. At higher temperatures, the catalytic activity drops. The decrease of activity is mainly due to a change of particle shape with the calcination temperature rather than to the increase of the particle size. At a calcination temperature of 200°C, the particles present small facets with rounded parts, and their outer surface contains a large proportion of low coordinated sites (steps and corners) while at high temperature of calcination, they are truncated octahedra with smooth facets.

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 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 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 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

By Gaby Steinbach

A novel synthesis is described for the preparation of supported gold catalysts for low-temperature CO oxidation. The novel route is a variation of the inverse co-precipitation method and requires amphoteric metal hydroxides, with zinc and aluminium hydroxides chosen. Catalysts were prepared by inverse co-precipitation (ICPa) and by the novel route (ICPb) and tested for CO oxidation at 60ºC. Preliminary results showed the novel route to be superior to ICPa; the catalysts prepared by ICPb showed higher catalytic activities. The effect on catalytic activity of parameters such as pH, calcination temperature, washing of precursor and calcined catalysts and ageing was investigated. A preparation pH of 9 and a Zn to Al mass ratio of 3 proved to be optimal. It was possible to remove residual chloride by washing thereby enhancing catalyst performance. Ageing and Mg citrate addition were also shown to improve catalyst performance. Characterization of the catalysts revealed that better activities were obtained when the support was more crystalline and had a higher surface area. The presence of carbonate-containing species in the support decreased catalytic activity. 197Au Mössbauer Spectroscopy revealed the presence of Au3+ when catalysts were heat-treated at temperatures of 200ºC and below. Catalysts calcined at 400º had 75% of the gold present as Au0, with the remaining gold present as Au3+.

Oct 1, 2003

By József L. Margitfalvi

Different Au/MgO catalysts modified with Mn, and Fe were prepared by precipitation-deposition. The catalysts were characterized by XRD, FTIR, Temperature Programmed Reduction (TPR) and CO chemisorption and were tested in CO oxidation in the temperature range of 243-523 K. The catalytic tests using both Temperature Programmed Oxidation (TPO) technique and time on stream (TOS) experiments revealed the high activity of catalysts prepared. In TPO experiments the modification by Mn significantly increased the activity above 300 K, however in the subambient temperature range the activity decreased considerably. Catalysts modified by iron did not show any decrease in the activity below 300 K, while the activity at high temperature increased significantly. Catalysts modified by Mn, Fe showed higher activity, selectivity and stability in preferential CO oxidation, carried out in the presence of hydrogen than the unmodified Au/MgO catalysts. Results of in situ FTIR spectroscopy on both the base Au/MgO and the iron modified catalyst unambiguously revealed the formation of ionic gold in the presence of CO/O2 mixture. The formation of this species was strongly hindered in catalyst modified by manganese. Results obtained strongly support the need for the formation of "metal ion - metal nanocluster" ensemble sites. These sites are involved in the activation of the CO molecule prior to its reaction with atomic oxygen. It is suggested that at subambient temperature these ensemble sites contain mainly ionic forms of gold, while at higher temperature iron or manganese ions are involved in CO activation.

Oct 1, 2003

By Lizelle Glaner

An investigation was carried out by Mintek to investigate the influence of additions of gold to ?Fecraloy?, alloys based on Fe-Cr-Al. The aim was to try and improve the oxidation resistance of the ?Fecraloy? alloys at elevated temperatures over extended periods of time. The ?Fecraloy? alloys are very oxidation resistant alloys already employed in industry as substrates for metallic catalysts in auto-catalyst systems for high performance cars. Since their life and durability is limited by the slow, but steady, oxidation of the substrates, any change in the growth or stability of the oxides could be an improvement.

Oct 1, 2003

By Peter Claus

In the last years, supported gold catalysts with particle sizes smaller than 10 nm have attracted a lot of attention. While gold bulk metal is rather inert in chemical reactions and, thus, is of low interest for catalysis, highly dispersed gold particles supported on oxides as TiO2 or ZrO2 show surprisingly high activities in some reactions important for the chemical industry. The oxidation of carbon monoxide at low temperatures is mainly used as model reaction to study the unusual properties of gold catalysts [1]. On the other hand, to evaluate the catalytic potential of gold, other chemical reactions which allow to control also the selectivity have to be considered. The selective hydrogenation of ???-unsaturated aldehydes to allylic alcohols is of both commercial relevance (e.g. in fine chemical and pharmaceutical intermediate production) and specific scientific interest [2]. Note that thermodynamics favors hydrogenation of the C=C over the C=O group (stronger negative free reaction enthalpy of 35 kJ/mol), and for kinetic reasons the C=C bond is more reactive than the C=O group. Thus, in the presence of most of the conventional hydrogenation catalysts, based on Pt, Rh or Pd, -unsaturated aldehydes such as acrolein and crotonaldehyde are hydrogenated predominantly to the saturated aldehydes and only to a minor extent to unsaturated alcohols. Therefore, it is desirable to find catalysts which are able to control the intramolecular selectivity by hydrogenation preferentially the C=O group while keeping the olefinic double bond intact (Fig. 1).

Oct 1, 2003

By Shinji Shirakawa

The gold wire bonding technology is widely used for electrically connecting aluminum pads on IC devices to external terminal of semiconductor. In 1960?s, the tensile strength of gold bonding wire was about 100 MPa only. However, recently the wire with 300 MPa in strength has been developed. Since the gold bonding wire was started to use for IC package in early 1960?, the many types of gold bonding wire has been developing continuously in order to meet market?s needs, such as high density, small size and thin type of IC packages. Moreover, electronic equipments were used in automobile applications and also demanded good reliability under severe temperature environment. Thus Au-Pd alloy wire has been introduced instead of the wire with 4N(99.99wt%) purity gold to provide excellent reliability in Au-Al bond interface. The phenomena at Au-Al interface in the high temperature storage have been already explained by several studies as follows. There are five phases of inter metallic compound (IMC) between gold and aluminum. Just after bond gold ball on aluminum pad, Au5Al2 phase was formed and occupied almost all of IMC area. During high temperature storage test, Au5Al2 phase transformed to Au4Al phase, then this phase was corroded by Bromide (Br) ion that was isolated from molding resin. Thus the reliability between Au and Al degraded. In case of Au-Pd alloy wire, the concentrated palladium phase (Au-Pd-Al) was formed at the interface between Au alloy ball and Al pad. The Au-Pd-Al phase prevented from transforming between Au and Al, therefore Au5Al2 phase was hard to transform to Au4Al phase. Consequently the reliability at the interface between Au alloy ball and Al pad was less degradation. However, in recent study using several advanced analysis technique, Au4Al phase was found at the interface between Au alloy ball and Al pad same as the case of conventional gold wire (4N purity gold bonding wire). It was suggested that the formation of concentrated palladium phase (Au-Pd-Al) related the excellent reliability at ball bonding process.

Oct 1, 2003

By Donka H. Andreeva

Gold catalysts based on different supports, titania, zirconia, ceria and mesoporous titania and zirconia, nonpromoted and promoted by vanadia in the reaction of complete benzene oxidation have been studied. XRD, HRTEM, TPR, Raman and ESR spectroscopy were applied for the characterization of the catalysts. The influence of gold on the reduction behavior, state and structure of vanadia on the surface was studied, as well as the role of supports nature on the properties and catalytic activity. A strong synergistic effect between gold and vanadia was observed for the all studied catalysts with an exception of the catalysts supported on mesoporous zirconia. In the last case the catalysts containing gold and gold-vanadia exhibit high and equal catalytic activity. The catalysts on ceria show highest and stable catalytic activity in the studied reaction among the all studied catalysts.

Oct 1, 2003

By Michael B. Cortie

The young field of nanotechnology has as its objective the design and construction of useful devices made of nanoscale materials. Objects or structures which have at least one important dimension in the range 0.5 to perhaps 50 nm may be considered to be in the nanoscale domain. These sizes lie far below the 200 nm or so that can be resolved with an optical microscope, and are closer in size to the 0.3 nm diameter of individual atoms. Nanotechnology, which is the study and exploitation of these tiny structures, is attracting keen interest at present. The excitement is motivated by the observation that control of matter at the nanoscale holds the promise of faster computing, better medicines, and smarter materials. In this paper, the physical phenomena on which this optimism is based are broadly discussed and explained. Where appropriate, examples of the rather different and curious properties of gold at the nanoscale are used to illustrate the points covered.

Oct 1, 2003