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By Andreea Catalina Gluhoi

The oxidation of propylene and methane has been investigated over two series of Au/MOx/Al2O3 and Au/MIOx/MIIOx/Al2O3 catalysts (M, MI, MII =Li, Rb, Mg, Mn, Ce, Zr). Whereas the effect of the presence of MOx or MOI x/MOII x on the oxidation of methane is relatively small, a large enhancement in activity is observed for propylene oxidation. Synergistic effects have been observed by combining ceria or a transition metal oxide (high oxygen storage capacity) with an (earth) alkali metal oxide.

Oct 1, 2003

By Philippe V. Scheers

Polycrystalline gold, glassy carbon and gold-activated glassy carbon electrodes were compared for the production of hydrogen peroxide by the cathodic reduction of dissolved oxygen. Gold was deposited on glassy carbon by sputtering with a sputter coater and by electrodeposition from a diluted KAuCl4 solution using short potential steps. The sputtered gold particles were not adherent enough, but there were no adhesion problems with the electrodeposited gold particles. The gold coverage of the glassy carbon surface could be varied by applying a different number of potential steps. The overpotential for the electroreduction of oxygen to hydrogen peroxide decreases with increasing gold coverage of the glassy carbon surface, and for gold coverages exceeding about 16 %, the overpotential is close to that observed on polycrystalline gold.

Oct 1, 2003

By Christina Graf

A synthesis of colloidal gold shell particles with a silica core is described. Small gold nanoclusters were attached to the functionalized surface of colloidal silica particles. Reductive growth and coalescence of these clusters lead to the formation of a closed gold layer. By variation of the thickness of this gold layer and the radius of the shell it is possible to adjust the plasmon resonance of the gold shell particles over the whole visible and infrared region of the spectrum. The optical properties of the particles made are in good agreement with theoretical calculations for coreshell particles. Due to their low polydispersity these gold shell particles form in solution large crystals with submicron lattice constants. It is also possible to produce hollow gold shells by dissolution of the silica core. A new method to coat the silica core gold shell particles with an additional outer silica shell is also presented. This allows due to a reduction in the Van-der-Waals forces to make more permanent dried crystals and facilitates functionalization of the particles for use in various photonic applications.

Oct 1, 2003

By Masayuki Ishikawa

In a radio frequency and optoelectoronic device packaging, Gold-Tin (Au-20 wt% Sn eutectic) solder is used widely due to the excellent electrical and thermal conductivity, high strength, and negligible creep characteristic under repetitive thermal cycling. With the recent lead-free movement, Gold-Tin solder is recognized as an alternative material for high temperature Lead-Tin solder. Generally, Gold-Tin solder is supplied in the forms such as ribbons, pellets, and ring frames. However, these forms must be set-up accurately on the joint area to press chips in bonding, therefore, it is difficult for these forms to satisfy the recent requirements for the down sizing in the connection areas. On the other hand, Au-20 wt% Sn solder paste can be applied flexibly to various supplying methods, such as printing, dispensing system and pin transcript. These methods also make it possible to reduce the production cost. However, in the case of using the solder paste, the void issue is one of the most undesirable problems. The void causes the degradation of the characteristics such as the bond strength, electrical characteristic and thermal conductivity. We have been intensifying the development of the void free paste, and have achieved void reduction by optimizing the powder size, the flux composition and the reflow condition.

Oct 1, 2003

By Christopher W. Corti

A major aim of the GOLD 2003 conference, is to promote new gold related science and technology with a view to developing new useful industrial applications for gold. Current industrial uses have provided a steady annual industrial demand for gold of around 350-400 tonnes in recent years, the bulk of which is centred on electronics applications, with dental uses constituting the second largest application. However, there is good reason to believe that whilst gold will continue to play a major role in these sectors in the future, substantial growth of demand is not anticipated. Increased industrial demand for gold is only likely to come through the emergence of new applications, probably most significantly in five broad market sectors: ? Pollution and emission control technologies, including fuel cells. ? New uses for gold in advanced electronics, electrical systems and devices. ? Chemical processing of a range of bulk and speciality chemicals, using gold based catalysts ? Advanced coatings exploiting the novel properties of gold, particularly in nanoparticulate form. ? New biomedical uses for gold including medical treatments, drugs, implants, sensors and devices. There is cause for optimism that many new applications for gold could emerge in these sectors over the next decade and that this will lead to a substantial growth in demand for gold. It is clear that many of these new opportunities will be based on a chemical approach to synthesis of useful products rather than what has historically been a materials or mechanical approach. To turn this expectation into reality requires sustained support of R & D and a determination to exploit this new science and technology into viable commercial applications.

Oct 1, 2003

By Yasuo Iizuka

We have had studied CO oxidation on unsupported Au powder (mean particle size, ca.100nm) manufactured by evaporating ultra high purity gold metal (>99.99%) in inert gas and reported that it showed some activity after oxidizing pretreatment in O2 at 423 K?453 K. However, recent XPS analysis of the Au powder revealed that it contains much amount of impurity metals such as Ag and In at levels which far exceed those expected from the impurity level of raw gold metal in the bulk. Several samples of Au powder containing different amount of impurity metals were prepared to examine whether the activity depends upon the existence of surface impurity or not. Activity measurements were performed at 273 K after undergoing the powder under various pretreatment conditions. Although the activity of Au powder varied to some extent according to the pretreatment condition, it is strongly correlated to the surface concentration of Ag. Such dependence was not found for In, indicating that the activity of unsupported Au powder is mainly due to the existence of Ag in the surface layer. The activity attributable to ?particle size effect? was not recognized for Au powder with a mean particle size larger than 80 nm.

Oct 1, 2003

By Andreas Zielonka

To meet the increasing demands of the quality and long term stability of technical systems also the applied materials have to full fill higher standards. This is of special importance where the function of a whole system depends on the reliability of the used materials for example for connector systems in automotive, computer and other electronic equipment?s. In most cases for connector systems electro deposited top layers are applied. To improve the quality of the applied layers new electro deposited systems are developed. One important field of research are the development of composite materials as dispersion coatings and multilayer systems. Multilayers are systems with a high number of single inter-layers of different metals or alloys with the wide chance of the alloy composition. As gold is one of the most important contact material for high quality connector systems it is used as basis for the development of multilayer systems. For the electrodeposition of multilayers two different methods can be applied, the single and the dual plating process. As in the dual plating process two different electrolytes are used, the single plating process allows the formation of multilayers from one electrolyte. In the presented research results cobalt and nickel are used besides gold for the formation of the multilayers. The properties of the layers can be influenced in a wide range by the change of electrolyte composition and the process parameters as current density, current waveform, temperature, hydro-dynamic conditions at the electrode surface and by the number and thickness of the inter layers of the deposited materials. The paper describes the fundamentals of the electro deposition of multilayer systems. For the investigation of the properties of the multilayers different techniques are applied. One of the most important parameter are the thickness of the total layer and of the applied sublayers. The thickness of the sublayers can be varied between a few nanometers up to micrometers. The wear resistance, the contact resistance and the plug-in forces are measured as these parameters are important for the technical application of such layers. For the description of the structure composition and surface properties the sample where also investigated by scanning electron microscopy (SEM), energy dispersive x-ray-analyses (EDX) and glow discharge optical spectroscopy (GDOS). The paper shows that the deposition of gold based multilayers is possible and that the properties of such systems can be varied in a wide range what opens new fields of applications of such materials.

Oct 1, 2003

By Inga Tuzovskaya1i

Three types of gold species were observed for gold-zeolites, prepared by reduction of ionexchanged Au species in a series of zeolites: (i) Au3+cations, (ii) neutral Au0 n or charged Aus+ n clusters suggested to be inside the zeolite channels, (iii) Au nanoparticles with diameter varied from 2 through 20 nm located on the external surface of zeolite microcrystals. Contribution of the gold species formed in zeolite after the ion exchange was found to depend on zeolite type, acidity of zeolite, temperature of reduction and time of storage of the exchanged and reduced Au-containing zeolites. Au3+ ionic species and clusters Aun were formed after the ion-exchange procedure (in contrast with the familiar production of Agn in same zeolites). Gold nanoparticles were observed only as the result of reduction of the Au-exchanged forms at elevated temperatures due to reduction of Au3+ species and aggregation of clusters.

Oct 1, 2003

By Rodolfo Zanella

Au/TiO2 catalysts prepared by deposition-precipitation with NaOH (DPN) (~3 wt%) and urea (DPU) (~8 wt%) were tested in crotonaldehyde hydrogenation at atmospheric pressure. There is no differences in activity (mole.gAu -1 s-1) and selectivity between both DPU and DPN samples for a given activation treatment. This is due to the fact that DPU and DPN samples exhibit similar gold particle size distribution, although the gold loading in DPU is much higher that in DPN. The DPU samples were reduced under H2 at different temperatures (120-500 °C) or under air at 300 °C with various flow rates, to vary the average particle size within a large range, 1.7 to 8.7 nm. The selectivity to crotyl alcohol (selective hydrogenation of the carbonyl bond) is high, 60-70 %, and almost constant as a function of the particle size. The selectivity to crotyl alcohol is also constant for conversions between 10 and 50%. These results suggest that the adsorption mode of crotonaldehyde is of ?3 or ?4-type. In contrast, the TOF depends on the gold particle size, it drastically increases when the gold particle size is ~2 nm. Our results are in agreement with former studies that suggest that the gold atoms involved in the hydrogenation process are those of low coordination.

Oct 1, 2003

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 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 Aalbert Zwijnenburg

One of problems connected with the use of gold/titania-based catalyst systems is the low yield in propene oxide (up to 2 wt %). It is shown that the low propene oxide yield is due to product inhibition. New options for propene epoxidation with hydrogen and oxygen are discussed. INTRODUCTION The direct gas-phase synthesis of propene oxide (PO), by the use of molecular oxygen, is still aimed for. Agbased catalysis is in principle possible, but selectivity at present is not promising. Highly dispersed gold on titanium containing catalysts show an extraordinary selectivity in the oxidation of propene to the corresponding epoxide (> 99 %), using a combination of H2 and O2 as oxidation mixture [1]. Additional studies of the epoxidation reaction have indicated several drawbacks of the Au/TiO2 catalyst. Firstly, the low conversion (1- 2 %) obtained under typical reaction conditions (atmospheric pressure, 323 - 423 K) cannot be increased by increasing the reaction temperature, because this leads to extensive by-product formation. Secondly, the low efficiency of hydrogen (relatively large amounts of water are formed) is hard to prevent. Finally, significant deactivation of Au/TiO2 catalysts within several hours on stream has been observed. Deactivation can be almost completely prevented by using dispersed TiO2 supports, such as TiO2/SiO2 and Titanium-Silicalite-1 (TS-1) [2]. In recent literature [2,3] a hydroperoxide-like intermediate has been proposed to be responsible for the selective epoxidation. This oxidising species is said to be formed over gold and subsequently used for epoxidation over the Ti-containing support. The support is responsible for the slow desorption of PO. One of the problems for future industrial application might be the low yield in propene oxide. Furthermore, the presence of minor amounts of by-products, not detected on lab-scale catalyst testing, might complicate the separation unit in an industrial process. The reason for the low PO yield over Au/TiO2-based catalysts will be discussed in this paper. Temperature Programmed Desorption (TPD) and micro-flow experiments have been carried out to study PO desorption and catalyst performance, respectively. A catalytic cycle is proposed together with its consequences for the maximum yield in PO. Finally, several process and catalyst options are discussed in view of potential future industrial application.

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