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By Mari Yamamoto

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

Oct 1, 2003

By Hua-Zhong Yu

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

Oct 1, 2003

By Renaud Cousin

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

Oct 1, 2003

By Kenji Koga

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

Oct 1, 2003

By Heidi Fauser

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

Oct 1, 2003

By Matthew S. Hall

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

Oct 1, 2003

By Anna Maria Venezia

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

Oct 1, 2003

By Gary Pattrick

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

Oct 1, 2003

By Jolanta Olkowska-Oetzel

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

Oct 1, 2003

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