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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 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 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 Ronald L. Bruening

IBC has developed a cost effective MRT process for the selective extraction and recovery of gold, copper, and a mixture of other base metals from mine leach cyanide solutions. This is a two-stage system in which the gold is first recovered selectively as a high purity salt. The copper is then recovered separately as a sulfate salt. The other base metals are then collected as a cyano anion concentrate. Three different SuperLig® materials are used. The first stage can be used alone on gold leach solutions where copper and other base metals are not a problem. The two or three stage system is used when the base metals build up in the leach solution, resulting in increased costs. The cyanide or cyanide/cyano anion concentrate can be recycled back to the leach solution until the build-up of other salts, etc. becomes too high, or this too can be controlled with a percentage bleed stream.

Oct 1, 2003

By Mari Yamamoto

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

Oct 1, 2003

By Hua-Zhong Yu

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

Oct 1, 2003

By Kenji Koga

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

Oct 1, 2003

By Matthew S. Hall

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

Oct 1, 2003

By 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 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 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 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