Search Documents

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 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 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 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 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 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 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 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 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

By Michael B. Cortie

Mesoporous gold sponge has the unique property of being both metallic and highly resistant to oxidation. It has potential application in catalysis, in bio-sensors, in optical coatings, in analytical chemistry and, as we show here, as the basis for a new kind of ultra-capacitor. Due to the cost of gold, the most probable niche for a gold-based ultra-capacitor would be in the high-power/high-energy regime, a region where gold would compete with devices based on RuO2. A high internal resistance limits the power that can be usefully drawn from existing carbon-based ultra-capacitors, and that this problem can potentially be overcome by gold-based devices. A simple proof-of-concept ultra-capacitor based on mesoporous gold is described and its behaviour during charge and discharge cycles examined. In this work a step change in the input or output voltage of the device was used as the controlling parameter. There was also a residual faradaic current resulting from traces of undissolved aluminium left over from the AuAl2 precursor used to make the sponge, and some charge storage due to polarization of the solution. Deconvolution of these three effects was not entirely accomplished, but an ostensible capacitance of about 7 to 14 mF/g Au was demonstrated. Further improvement from these early results seems likely.

Oct 1, 2003

By M. Kinne

Catalyst preparation/ characterization Slightly modified DP (~Schumacher et al. Catal. Lett. 89, 109, 2003) CeO2 HAS 15 from Rhodia calcined in air for~ 2h BET: ~188m2/g, particles size: 5.7nm (TEM, XRD) + HAuCl4 at pH of 6.5-7, (>95% of the Au was deposited) ? Au/CeO2 (2.6wt% Au, ICP-AES) A new conditioning procedure was applied, including heating at low temperature in N2 and H2/N2 mixtures) Patent DE 10205873A1. Very small Au particles <2nm, for CO oxidation catalyst as Au/TiO2, Au/Fe2O3, and Au/Co2O3 Here Au particles size <3.5nm (XRD) Summary ? CO is nearly exclusively adsorbed on the Au particles ? Positive reaction orders of 0.5 are found for CO and H2O ? Ea= 40kJ/mol ? The catalyst is very active and stable ? During WGS reaction huge amounts of formates are formed and cover the surface ? The activity of the catalyst seems to be correlated with the formate species.

Oct 1, 2003

By Laura Prati

Gold-on-carbon catalysts resulted very active and selective in liquid phase oxidation [1, 2, 3] and during past studies we established that activity is ruled by two factors: particle dimension and gold exposure on the carbon surface [4]. These two parameters are also connected to the nature of activated carbon where the chemical nature of the surface oxygenated groups probably plays an important role [5]. Our studies, focused on the design of an active gold-on-carbon catalyst for liquid phase application, were aimed, operating a fine tuning of all the parameters involved in determining activity, to optimize gold-on-carbon preparation, keeping in mind that gold particle activity increases with decreasing particle size and increasing gold exposure. Gold sol immobilisation represents a versatile methodology in preparing gold catalysts [6]: throughout this work we used as sol stabilizing agent, the N-dodecil-N,N-dimethyl-3-amino-1-propan sulphonate (SB), that provides both sterical and electrostatic stabilisation, a condition we already demonstrated necessary to preserve particle dimension when carbon is used as the support [6]. We generated different gold sols by varying the relative amount of reagents (HAuCl4, SB, NaBH4), the type of alkali and the temperature of the gold precursor reduction. Moreover, as we had recently evidenced that there is also a carbon effect [5], we employed only one active carbon to immobilize the sols.

Oct 1, 2003

By Olaf Andersen

Crucible melt extraction yields short metal fibers with eqivalent diameters as low as 50 µm from almost arbitrary metals and alloys. Highly porous components can be made from such fibers by suitable deposition and sintering methods. This technology is being developed at the Dresden based Department of Powder Metallurgy and Composite Materials of the Fraunhofer Institute for Manufacturing and Advanced Materials (IFAM) and has been applied to gold alloys and iron-base alloys containing small additions of precious metals. From the manufactured gold fibers, sintered structures were made for decorative applications. Additionally, it was found that due to rapid solidification during the fiber formation, precious metals can be finely dispersed in ironchromium- aluminum (FeCrAl) and FeAl20 alloys. Good catalytic activity at elevated temperatures was found in compositions containing 3 wt.-% Ce and 0.5 wt.-% Pt.

Oct 1, 2003

By Jörg Fischer-Bühner

Conventional 22ct Au jewellery alloys are comparably soft in the as-cast and soft-annealed state and hardening by cold-working is the only way of giving strength to the jewellery. The paper first focuses on hardening of 22ct jewellery alloys by conventional means, i.e. solid solution hardening with base metals (aiming particularly at an increased as-cast hardness) as well as precipitation hardening by alloying with base metals beyond the solubility limits and subsequent age-hardening heat treatment. Co-additions of ~2% turned out to result in most pronounced solid solution hardening up to ~100 HV1 in an investment cast & quenched state. Subsequent heat treatments, consisting of solution annealing at 850°C for 1h followed by water quenching and ageing at 300°C ? 400°C for ~ 1h lead to pronounced age-hardening with a peak hardness of ~ 260 HV1. In contrast, 22ct Au alloyed with Ni, Fe or Sb display no age-hardening effect within the same range of heat treatment parameters. The 2nd part of the paper reports on some preliminary trials to enhance the hardening effect of the base metals by additions of suitable elements, which possess a strong tendency to phase formation with the added base metal during ageing treatments. It is shown, that the age-hardening behavior of 22ct and 990/995 Au alloyed with Co or Ni can be remarkably influenced by additions of Sb. A total of only 10wt%0 of CoSb or NiSb-additions lead to a peak hardness of ~ 150 HV1 for a 22ct Au and ~ 100-120 HV1 for 990 Au , which is obtained already after very short ageing times (20-40min) at 300-400°C after solution annealing at 700°C / 1h / water quenching. It is suggested that the age-hardening mechanism in these alloys consists in precipitation of intermetallic CoSb- and NiSb-phases.

Oct 1, 2003

By Franz Simon

Conventional fine gold electrolytes for barrel applications working electrolytically actually permit significant precious metal savings by corresponding optimizations but the most gold is still deposited on areas of the components where it is not absolutely essential for the desired bonding and soldering applications, i.e. in high current density areas. Therefore an electrolyte working electrolessly has been developed which inevitably leads to a much more uniform thickness distribution since in an electroless process there are no areas favoured by metal deposition and current distribution. The new electrolyte will be presented and its performance will be compared with conventional electrolytes as regards thickness distribution. The potential gold savings will be discussed.

Oct 1, 2003

By Benedetto Corain

The production and dispersion of metal nanoclusters onto inorganic supports and amorphous carbon rest on well consolidated technologies belonging to the realm of industrial catalysis and of basic catalysis research (1). In spite of the existence of a variety of specific synthetic strategies, their very rationale relies on three main approaches i. e.: A: precursors of both the metal nanoparticles and of the relevant supports (or the support itself) are intimately mixed (even let to react) at ambient conditions and then thermo-reduced according to very controlled protocols (2); B: precursors of metal nanoclusters are let to be adsorbed onto suitable supports from the gas or liquid phase and subsequently thermally decomposed (3); C: metastable size-controlled metal nanoclusters are previously generated in a liquid medium and subsequently transferred onto pre-formed support particles (4). The production and dispersion of metal nanoclusters onto organic soluble supports is also a rather well documented academic praxis (5, 6, 7, 8) able to provide e.g. size-controlled Au0 nanoclusters of 4.4±1.7 nm (5). Our group started in 1997 developing (9) an innovative approach to the synthesis of metal nanoclusters dispersed inside insoluble, albeit accessible (see below) mechanically robust gel-type resins (10), which procedure was tested so far on palladium metal. Metal ions are previously dispersed upon ion-exchange inside of the polymer framework, followed by chemical reduction and by the aggregation of born metal atoms into nanoclusters, the size of which is templated (11, 12) by the three-dimensional intercommunicating meshes that build up the overall polymer framework (Figure 1).

Oct 1, 2003

By Timothy W. Ellis

Wire Bonding is the dominant IC interconnection process presently used in the semiconductor assembly industry (1). The flexibility, adaptability and cost of wire bonding will continue to keep it as the key process for the interconnection of integrated circuits to substrates. However, wire bonding still has certain technological hurdles to overcome if it is to continue following the semiconductor roadmap (2). Particular issues which need to be addressed include low overall tensile strength, low elastic modulus, low shear per unit area and mechanical loop stability of Gold based micro-alloys. The ability to produce ?Deformation Process Metal-Metal Matrix Composites? (DMMCs) is based upon the deformation nature of immissible metallic systems. For reference, the Gold (Au)-Molybdenum (Mo) phase diagram is shown in Figure 1 (3). By inspection of the diagram, Au has a very low solubility for Mo, while Mo has essentially no solubility for Au. This is the metallurgical analog of oil and water. In the Au-Mo case, this is particularly troublesome when producing precursor ingots of the alloy to be formed into wire products. In Table 1, the melting points and densities are shown for Au and Mo. As shown, the melting point of Mo is significantly higher than Au, and is very close to the boiling point of Au (2856°C). However, Au?s density is higher than that of Mo. As such, conventional casting techniques are not suitable, since solid Mo would float off the surface of an Au melt thus depleting the matrix of its alloy addition. In this work, two-phase composite wires were produced by deformation processing to develop an interconnection wire with elevated tensile strength, modulus and shear to those commonly available in the market (4). This technology has been used previously in the production of high strength electrical conductors particularly for high field pulsed magnets (5).

Oct 1, 2003

By Hannu J. Häkkinen

Metal clusters exhibit unique size-dependent physical and chemical properties that differ from those of bulk materials or large particles. Here we discuss recent theoretical investigations of the catalytic properties of free and MgO-supported gold clusters. The catalytic activity of gold clusters depends sensitively on the environment, charge state, and chemical composition of the catalyst. Relativistic bonding effects stabilize large planar structures for gas-phase gold clusters, and non-compact ?quasiplanar? structures are present as important isomers also for surface-supported clusters. The hybridization of the atomic 5d and 6s states is significantly enhanced by the relativistic effects, and large spatial variations in the nature of the local electronic structure make the low-coordinated gold atoms preferable adsorption sites for oxygen molecules. The adsorbed oxygen molecules are activated to superoxo- and peroxo-states via charge-transfer from gold, and Eley-Rideal and Langmuir-Hinshelwood reactions with CO proceed via low-barrier formation of intermediates, which do not require O-O dissociation as precursors. This facilitates the low-temperature (below 300 K) activity of gold nanocatalysts in CO oxidation. Other gold nanostructures, such as mono-atomic gold nanowires, may also become important prototype systems in chemical sensing and nanocatalysis; here we show that they are active promoters of hydrogen dissociation.

Oct 1, 2003