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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 Emile D. L. Rienks

We have studied the interaction of NO with the quasi-hexagonally reconstructed Au(100) surface. Using variable temperature scanning tunneling microscopy we have observed formation of the unreconstructed phase of Au(100) after NO exposure. This NO adsorption induced phase transition is observed in a window of temperatures around 170 K. Under the same conditions, CO and O2 cannot drive the phase transition, suggesting weaker interaction. Thermal desorption spectroscopy experiments provide an estimate for the strength of NO chemisorption on Au(100) of 57 ± 4 kJ mol-1.

Oct 1, 2003

By Ayako Iwakoshi

Highly concentrated pastes of gold nanoparticles were successfully produced by use of a special kind of protective polymer and a mild reductant. Solid part of the pastes consists of up to 85wt% of gold nanoparticles, 10~30 nm in diameter, and residual protective polymer. This component can be diluted by any kinds of solvent at arbitrary rates. Electronics, optics, catalysts, colorants and surface metal coatings are possible application fields. 1. Introduction Noble metal nanoparticles are of interest in a variety of fields ? such as colorants, metal coatings, electronics(1), optics(2), and chemical catalysis(3). Especially, in the color field, the gold nanoparticle has been known as an aesthetic red colorant for stained glass and fine glassware, such as Venetian glass. The mechanism of coloring is attributed to surface plasmon absorption of gold nanoparticles(4,5). The gold nanoparticle in stained glass shows very clear red color, which is very durable for hundreds years. On the other hand, the red color of organic pigment in paint films often fades away within several years. We intended to reproduce the elegant and stable coloring of stained glass in paint films. In order to color a very thin, 20~50?m, paint film like stained glass, production of highly concentrated dispersion of gold nanoparticle is necessary. To achieve this, there were two issues to be overcome. One is how to prevent the coagulation of gold nanoparticles in highly concentrated solution. So far, several methods to prepare gold nanoparticles(6,7) were reported. But only a few methods succeeded to stabilize the gold nanoparticle dispersion at higher concentration than ppm order. The other is controlling of the particle size, this is because the color of gold nanoparticles is very sensitive to the particle size. Only when the particle size lies around 10 nm, the suspension exhibits red color like stained glass.

Oct 1, 2003

By Fabian Mohr

The methyl substituted binuclear cyclometallated gold(I) complexes [Au2(?-n-MeC6H3PPh2)2] [n = 4, 5 and 6] all undergo oxidative addition reactions with halogens and, in the case of the 4- and 5-methyl substituted analogues, with dibenzoyl peroxide to give metal-metal bonded digold(II) complexes [Au2X2(?-C6H3-n-MePPh2)2]. The 4- and 5-methyl substituted digold(II) compounds on warming or exposure to light undergo carbon-carbon coupling reactions to give gold(I) complexes containing the corresponding 2,2'-n,n'-biphenylyldiphenylphosphines. The 6- methyl substituted digold(II) complexes rapidly isomerise above ca. -20° C to binuclear heterovalent gold(I)/gold(III) compounds [XAu(?-2-Ph2PC6H3-6-Me)AuX{?2-(6-MeC6H3-2-PPh2)}], containing a fourmembered cyclometallated ring on a gold(III) centre. Surprisingly, no carbon-carbon coupling could be induced for any of the 6-methyl substituted compounds, even under forcing conditions. This difference in reactivity of the 6- methyl derivative, compared to that of the 5-methyl and unsubstituted analogues was studied by ab initio calculations using a series of model compounds. The results are in excellent agreement with the experimental findings and suggest that the key-step in the C-C coupling reaction is the partial opening of the Au(III)-P bond in one of the transition states. In the 6-methyl system this transition state is energetically inaccessible and hence no C-C coupling occurs.

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 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