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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 Jorge M. C. Soares

The CO oxidation reaction has been studied on Au/TiO2 catalysts prepared by incipient wetness (IW) and deposition-precipitation (DP) methods. Additionally the assessment of activity was also conducted on simple gold compounds (Au2O3 and Au(OH)3) and their physical mixtures with TiO2. We have found that there are three types of CO2 production from fresh catalysts, which are only dried, namely: Non-catalytic Type I (low temperature CO2 production); Non-catalytic Type II (higher temperature CO2 production) and Catalytic Type III. The DP catalysts are far more active for Type III reaction, showing activity already at room temperature, whereas the IW catalysts generally do not show steady state conversion until T>673 K. This is due to both large particle size and the presence of residual chlorine for the latter. No truly catalytic activity was found for low temperature CO oxidation on gold precursors on their own, although both Au2O3 and Au(OH)3 react well with CO even at room temperature in an irreversible manner (Type I reaction). Despite that, catalytic activity was obtained by mixing Au(OH)3 or Au2O3 with TiO2 which gives further emphasis on the importance of a good contact gold/support and the absence of chlorine.

Oct 1, 2003

By Rainer Süss

An investigation was carried out by Mintek to investigate the influence of a range of alloying additions (vanadium, cobalt, zirconium, antimony and germanium) on the formability and hardenability of alloys with gold content >90 wt%. This paper reports on the hardening mechanisms that can be utilised to increase the hardness of gold (>90 wt% Au) by conventional alloying, as well as the hardening effect obtained by alloying with specific elements. Preparation methods for the alloys are described, which include the steps of melting, annealing, quenching, cold working and age hardening. Focus is given specifically on alloys that were developed at Mintek with a gold content >90 wt%, which are not only harder, but exhibit good resistance to tarnishing and corrosion.

Oct 1, 2003

By V. Caps

Gold has been often used as an alloying component in order to increase or modify the catalytic properties of an active metal. For example, in the hydroconversion of methylcyclopentane, Riahi et al [1] shown that the addition of gold to palladium or platinum enhances the activity which becomes greater than that of the pure metals whereas the selectivity towards products resulting from ring expansion increases. Molenbroek et al [2] presented a detailed study on Ni-Au catalysts which exhibit activity for steam reforming and have been proved to be more resistant toward carbon formation than the pure Ni catalysts. Blocking of highly reactive Ni edge and kink sites by Au atoms is assumed to be the reason for the increased robustness of the Ni-Au catalyst. Nevertheless, the own catalytic properties of pure gold have been almost ignored up to the pioneering work of Haruta et al [3] which demonstrates the high activity of gold for CO oxidation at low temperatures. Other reactions such as WGS reaction, propylene epoxidation or benzene total oxidation have then been shown to be catalyzed by gold [4]. This discovery induced the publication of papers devoted to analyze the different factors controlling the activity of gold catalysts. Among them the most relevant appears to be the gold particle size, the nature of the support [5] and the preparation methods [6]. Clearly distinguish between support and size effect is not straightforward. Indeed, the calcination step often needed to synthesize supported catalysts on different supports, leads to different particle sizes showing that particle size and support are interdependent. To circumvent this difficulty, Au-based supported catalysts have been synthesized by using laser vaporization and low energy cluster beam deposition. The as prepared catalysts have then been characterized and tested in CO oxidation reaction.

Oct 1, 2003

By Michael Hopp

The beginning of the electroforming technology dates itself on the beginning of the industrial revolution 1800 to 1820 approximately. Basis was the existence of electricity in order to be able to drive the electro-form-process. With the development of the electroforming, big names of the science-history, like Michael Faraday (1791? 1867), Sir Humphry Davy (1778?1829), Max Schlöter (1878?1946), Werner von Siemens (1816?1892), and many others. Already about 1840, the first monograph originated to electroforming (38). While in the first years the electro-forming most extensive only to the coating of art - or other usefulness-objects was used. At the beginning of the 20th century the formation of objects from pure metals became more and more, later also from alloys to application. One of the first bigger electroforming factory, the ?Württembergische Metallwarenfabrik? was working 1894 in Geislingen / Steige, Germany. In the industrial application, the electroforming-technology is to be imagined away for miscellaneous coatingtasks and the form-body-preparation no longer today (18). A little bit confusing is the german name ?galvano-technology?. It based on the Italian physiologist and naturalist Luigi Galvani (1737 ? 1798). This technically seen is however wrong, right, the name is electroforming. The physical bases were founded mainly by Michael Faraday and Sir Humphry Davy.

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 Maria Agostina Cinellu

Some aspects of the reactivity of the two different kinds of gold(III) oxo complexes [Au2(N,N)2(?-O)2][X]2 [N,N = 2,2'-bipyridine (bipy) (1), 6-alkyl-2,2'-bipyridine (bipyR) (2), R = Me a, CH2Me b, CHMe2 c, CMe3 d, CH2CMe3 e] and [Au2(C,N,N)2(?-O)][X]2 [HC,N,N = 6-benzyl-2,2'-bipyridine (bipyR') (3), R' = CHMeC6H5 a, CMe2C6H5 b] (X = BF4, PF6) have been studied. Treatment with water converts the unsubstituted bipyridine complex [Au2(bipy)2(?-O)2][PF6]2 (1) and the cyclometallated derivatives [Au2(C,N,N)2(?-O)][PF6]2 (3) into the water soluble monomeric hydroxo species [Au(bipy)(OH)2][PF6] (4) and [Au(C,N,N)(OH)][PF6] (5), respectively. These hydroxo species, likely the intermediates in the formation of the oxo complexes, are quantitatively reverted to the latter ones by reflux in anhydrous solvents. Both kinds of oxo complexes react with PPh3 to give OPPh3, the gold(I) complex [Au(PPh3)2][PF6] and the free bipyridine ligands. The reaction of the dioxo complexes [Au2(bipyR)2(?-O)2][PF6]2 (2a, 2b, 2c, 2e) with different alkenes gives the unprecedented alkene complexes [Au(bipyR)(?2-alkene)][PF6]. The styrene adduct [Au(bipyip)(?2- CH2=CHPh)][PF6] (7) (bipyip = 6-iso-propyl-2,2?-bipyridine c) has been characterized, inter alia, by X-ray diffraction analysis. Organic products arising from olefin oxidation are also found in the reaction mixture.

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

By Jun Shan

The preparation of poly(N-isopropylacrylamide)-monolayer-protected clusters (PNIPAM-MPC) of gold nanoparticles was carried out in a homogeneous phase using three ways, in which three types of PNIPAM ligands were employed. The first type comprised of PNIPAMs with narrow molar mass distributions, synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization and thus, bearing a dithiobenzoate at the chain end. These polymers were used directly to passivate the gold nanoparticles upon the Schiffrin reaction in a one-pot synthesis. The second type of ligands was derived from the first one through hydrazinolysis, and they therefore contained a thiol end group. The third type of ligands was PNIPAMs obtained through conventional radical polymerization, post-modified to contain thiol end groups. The PNIPAM-MPCs were characterized by high-resolution transmission electron microscopy, and by dynamic light scattering. The one-pot synthesis utilizing the ligands of the first type turned out to be a simple and facile method, compared with the other two ways, with which the size of the gold nanoparticles can be easily manipulated mainly by adjusting the molar ratios of PNIPAM / HAuCl4. PNIPAM is a more efficient ligand to stabilize the gold nanoparticles in water and in organic solvents than alkanethiols. The surface density of PNIPAM chains ranged from 1.8 to 3.6 chain/nm2, which is much lower than that typical for alkanethiols. The thickness of a PNIPAM monolayer bound to the gold core is somewhat larger than the size of the random coil of corresponding free PNIPAM in aqueous solution, which suggests that the conformation of a PNIPAM chain bound to the gold core is to extended.

Oct 1, 2003

By Daven N. Compton

The optical properties of Au nanoparticles have been known for some time, with both Au colloids and Au nanoparticles embedded in glasses having been extensively studied. In this study, Pt nanoparticles have been incorporated into Au colloids, and the linear and non-linear optical properties investigated. UV-VIS spectrophotometry, fluorescence spectroscopy and the z-scan method have been used to examine the effects of such additions.

Oct 1, 2003

By Lorna Ortiz-Soto

A series of titiania- and silica-supported Au, Pt and Pt-Au catalysts prepared through different synthetic routes have been investigated in terms of their structural properties, adsorption of CO, and catalytic activity for the selective catalytic reduction of NO by propylene and the oxidation of and CO. Catalysts prepared by incipient wetness impregnation from individual Pt and Au precursors, exhibited characteristics very similar to those of monometallic Pt catalysts. This behavior is consistent with a model in which the two metals remain segregated due to their miscibility gap, and only Pt participates in the adsorption of CO and the reactions under consideration. In contrast, catalysts prepared from a Pt2Au4(C=CtBu)8 organo-bimetallic cluster precursor exhibited different behavior both in terms of CO adsorption and their catalytic activity for the three reactions examined. The combination of the kinetic, spectroscopic and structural characterization data suggests that in this case Pt and Au remain intimately mixed in the form of Pt-Au bimetallic particles, and that the presence of Au modifies the behavior of Pt.

Oct 1, 2003

By Noko S. Phala

The energetics of CO and CO2 hydrogenation to methanol were studied on a gold surface via periodic and cluster DFT calculations. CO hydrogenation appears to be much easier than CO2 hydrogenation on an Au(111) surface. The use of a cluster model does not seem to improve the energetics of CO2 hydrogenation. It is concluded that an active support (e.g. ZnO) will be required to increase the productivity of a gold surface towards synthesis gas conversion. The energetics of CO and H2 adsorption are improved on the cluster model compared to a slab model of an Au(111) surface, suggesting that nanosized gold particles may be beneficial in CO hydrogenation.

Oct 1, 2003

By Hiroaki Sakurai

Using batch reactors equipped with CO and CO2 gas sensor, CO oxidation over Au catalysts in room air has been investigated and compared with Pt catalysts. For both Au and Pt catalysts, the logarithm plot of CO concentration data during initial 10 min are well fitted by straight line, which mean the first order dependence on the CO concentration between 10 and 10,000ppm. The rate constant value (k) over Au and Pt catalyst generally decrease with increasing initial CO concentration above 100ppm. The value decrease especially rapidly between 100ppm and 1,000ppm over Pt catalysts, which should be due to the strong adsorption of CO on Pt. The k value over Au catalyst has become ten times or more as large as the Pt catalysts at 1,000ppm. Already for the initial concentration of 100ppm CO, the strongly adsorbed CO on Pt metal has been clearly observed by FT-IR during the reaction over Pt/Al2O3. A part of the strongly adsorbed CO has been remained on Pt after the disappearance of gas phase CO, and has gradually changed to gas phase CO2. Such strongly adsorbed species on Au has never been observed on Au/TiO2 under the same reaction conditions. These features of Au catalysts are favorable for indoor air purification.

Oct 1, 2003

By Masatake Haruta

Gold can be deposited as nanoparticles on a variety of support materials by coprecipitation or deposition-precipitation of Au(OH)3, grafting of organo-gold complexes such as dimethyl-Au(III)-acetylacetonate, mixing of colloidal Au particles, and vacuum deposition. Owing to the moderate adsorption of at least one of reactants (for example, CO) on the edges and corners of Au nanoparticles and to the activation of the counter reactant (for example, O2) at the perimeter interface with the supports, supported Au nanoparticle catalysts exhibit unique and practically useful catalytic properties at relatively low temperature below 473K. They have already been commercially used for deodorizers in rest rooms in Japan and will find growing applications in indoor air quality control, pollutant emission control, production of hydrogen energy carrier, and innovations in chemical processes. Cluster science of Au may also open an exciting area of research showing some magic numbers for dramatic changes in reactivity.

Oct 1, 2003

By Heinrich Möller

The electro-oxidation of 0.1 M ethylene glycol at gold, platinum and gold-platinum alloy electrodes in different heat treatment conditions has been studied in 0.5 M NaOH, at room temperature. Poisoning of all the electrodes occurs. However, the alloy electrodes poison at a faster rate than the pure gold and platinum electrodes. This indicates that the initially higher activity of these electrodes cannot be the result of decreased poisoning through a "third-body" effect.

Oct 1, 2003

By László Guczi1

Nanosize model gold particles with varying size were fabricated by deposition of a 10 nm thick gold film onto SiO2/Si(100) substrate by electron beam evaporation followed by modification using low energy Ar+ ion bombardment. The change in particle size were monitored by the Au 5d valence band states determined by ultraviolet photoelectron spectroscopy (UPS). The gold/iron oxide interface was studied by iron oxide deposition on gold. It was found that the energy profile of Au 5d valence band states are strongly redistributed with decreasing the gold particle size mostly affecting at the lowest and at the highest binding energies. The size effect in the UPS spectra can be interpreted by the energy redistribution rather, than by narrowing the 5d states. The iron oxide deposition increases the catalytic activity in CO oxidation whether it is on gold nanoparticles or on a continuous 80 nm thick gold film. The activity enhancement is significantly larger in case of gold nanoparticles. The interface interaction is operative in enlargement of the catalytic activity even if gold particles are not exposed to the surface, but they are located below the iron oxide layer.

Oct 1, 2003

By Antonio Laguna

During the past few years, synthetic efforts have been addressed to the synthesis of polymeric materials with optical or semiconducting properties or even with capabilities to act as sensors for volatile organic compounds (1). The most recent studies have been concerned with the synthesis of heterometallic systems with short metal-metal interactions and the determination of their optical properties. These complexes are undoubtly interesting from a theoretical viewpoint and include an emerging class of luminescent materials, in which the observed luminescence results mainly from the interactions among the different metal centers, as well as the environments of these atoms. The understanding of the photophysics and photochemistry of these products could permit the design of complexes with appropriate metals and ligands chosen for individual applications. Following a synthetic strategy consisting on reactions between acid heterometal complexes and basic gold precursors we have succeded in synthesizing supramolecular assemblies formed via acid-base stacking, which display tunable luminescence or selective and reversible sensitivity to Vapour Organic Compounds (VOC?s) (2-5). In this sense, in accord with previous Mössbauer studies carried out in the gold precursor complex [AuR2]- (R = C6F5), the basic properties of this and related materials have been employed as building blocks of supramolecular assemblies in their reactions with complexes in wich the metallic centers act as lewis acids as, for instance, Tl(I) or Ag(I) (6). For instance, in the case of silver, by reacting equimolecular quantities of [NBu4][Au(C6F5)2] with AgClO4, in acetone, a solid of stoichiometry [Au2Ag2(C6F5)4(OCMe2)2]n is obtained. The polymeric nature of this material in solid state is confirmed through X-ray analyses (figure 1). It consists of polymeric chains formed by repetition of Au2Ag2 moieties linked through short gold-gold interactions. Nevertheless, in solution, the nature of this polymeric materials was still a matter of controversy and, in this case, the optical properties have been shown as useful tools in order to obtain information. Thus, while dilute acetone solutions of this complex give a emission coming from pentafluorphenyl localized ??* excited states, in accord with the presence of isolated tetranuclear Au2Ag2 units, when the measurements are done at different and higher concentrations, a band that does not obey the Lambert-Beer law appears. This deviation is consistent with molecular aggregation in solution of these units through gold-gold interactions, and a clear correlation between the emssion wavelength and the structure in the solid state and in solution is shown (figure 2). DFT calculations accord with the observed experimental behaviour and show the nature of the orbitals involved in each transition.

Oct 1, 2003

By Jr. Fackler

The ionization potentials of gaseous Group 11elements are similar, with Au(0) being 1.5 eV greater than the next highest member of the group, Cu(0). The ionization potentials are all very much greater than the alkali metals, making these ?coinage? elements rather unreactive to chemical oxidation. Ionization from the first oxidation state shows a different pattern, with Ag(I) being the most difficult of the Group 11 ions to lose an electron. Gold(I) is noble and only normally oxidized in the presence of strongly coordinating ligands such as thiols or cyanide. Gold(I) compounds are 2-, 3- and 4- coordinate, with 3-coordinate species generally showing visible photoluminescence under UV excitation. Dinuclear Au(I) compounds with strongly coordinating S or C ligands can be oxidized to form isolable metal-metal bonded Au(II) compounds which are often readily isolable. Many have been structurally characterized. T he ease with which electrons are lost from closed shell dinuclear sp ecies (with anti-bonding M-M interactions) increases when metalmetal bonded compounds are formed. T his observation was made by our group with oxidative-addition studies of dinuclear gold(I) ylide complexes. It was superbly demonstrated recently by Cotton?s group who reported the isolation and characterization of a dinuclear closed shell transition metal species which is more readily oxidized than cesium. Trinuclear Au(I) pyrazolates, TR(pz), carb eniates, TR(carb), and benzylimidazolates, TR(bz), are well known and undergo electron loss through oxidative addition forming Au(I,III) mixed valence species and ultimately trinuclear Au(III) species. Au(II) species are absent from isolation in these oxidations. These carbeniates and benzylimidazolates also are excellent bases for metals ions such as Tl(I) and Ag(I). The acidic, neutral trinuclear compound [Hg(C6F4)3]3 also interacts with these bases. We have also shown that the neutral organic pi acids C6F6 and TCNQ form stacked pi-acid pi-base products with the trinuclear Au(I) compounds. In this paper, the structure of the octafluoronaphthalene acid-base product will be described. It displays a feature not observed previously in that the product is photoluminescent with a bright yellow emission. The 3.5 ms lifetime is very long and reminiscent of the long lifetimes observed by Balch for the stacked methyl,methoxy Au(carb). The electrochemical oxidation of tetragold(I) clusters, [Au4(form)4] have been studied in 0.1 M Bu4NPF6/CH2Cl2 at Pt working electrode at different scan rates. Three waves are obtained at 0.75, 0.95, and 1.09 V vs Ag/AgCl at scan rate 500 mV/s. The potential of the three reversible waves is independent of the scan rate in the range 50 mV/s to 3 V/s. The current at the third wave is larger than those at the first two waves. These tetranuclear species app ear to be effec tive catalyst precursors for the oxidation in air of CO. Introduction. The electronic structural relationships of the coinage elements and the alkali metals are similar in the sense that each have a [closed shell]ns1 configuration, yet their ionization energies (Table) and chemistries are clearly vastly different. The Group 11coinage elements have an underlying nd10 level immediately below the ns1 level. Unlike the alkali elements, ionization leaves the filled d electron shell the next accessible for further ionization. The coinage elements are all relatively ?noble?, much less reactive to environm ental conditions than the alkali metals. With the coinage elements, oxidation becomes very much dependent upon the types of ligand s availab le to bo nd to the ionized state.

Oct 1, 2003