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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 Masatake Haruta

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

Oct 1, 2003

By Heinrich Möller

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

Oct 1, 2003

By László Guczi1

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

Oct 1, 2003

By 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 Oleg G. Tovmachenko

We have studied optical properties of fluorescent nanoparticles. These particles consist of a metal (gold/silver) core, an empty and a dye labelled silica shells. The different dye molecules with moderate quantum yields (about 0.3) has been used. Almost all of types of nanoparticles show fluorescence enhancement. This enhancement is strongly dependent on the degree of the overlap between the surface plasmon band of the metal and the absorption/emission band of the dye molecules. The results are interpreted in terms of competition between local field enhancement and quenching of fluorescence by the metal surface.

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 Fabio Terzi

In this investigation some preliminary results are reported about the electrochemical oxidation of CO using goldbased encapsulated nanoparticles grafted on conducting substrate. The investigation has been planned in four steps: 1. production of Au(111) substrate and modification with self assembled monolayers; 2. synthesis and embedding of nanoparticles; 3. grafting of encapsulated nanoparticles on electrode substrates; 4. investigation of CO electroxidation on the modified electrode. The systems were characterized by means of various techniques (spectroscopic, microscopic, and electrochemical methods), obtaining information about SAM&apos;s structure and morphology, size and composition of nanoparticles and electrochemical behavior of modified electrodes.

Oct 1, 2003

By Eiichiro Mizushima

Catalyst systems comprising (Ph3P)AuCH3 and acid co-catalysts were found to be highly efficient for hydration of alkynes to give ketones. Methanol was the best choice of solvents. Introduction Hydration of carbon-carbon unsaturated bonds is one of the environmentally benign routes to the carbon-oxygen bond formation. Hydration of alkynes forming carbonyl compounds, an important variation in this category, is a well known reaction which has been extensively studied. The reaction by acid-catalysis is the most conventional method, while it is applicable only to electron rich acetylenes to obtain satisfactory yields (1,2). The hydration of simple alkynes usually requires another catalyst (co-catalyst), typically a mercury(II) salt (3), which is inconsistent with the guiding principle of Green Chemistry (4).

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

By Michele L. Kimble

A fast-flow reactor mass spectrometer has been utilized to investigate the reactions of gas-phase gold cluster anions with CO and oxygen. Addition of CO to Aun - produces species of the form Au(CO)m -, where m = 2-5. However, CO does not bind to Au2 - or Au3 -. With oxygen addition in the cluster source, gold oxide species with both molecular and atomized oxygen are produced. The addition of carbon monoxide to these preoxidized gold cluster anions reveals that select species with 1, 2, and 3 gold atoms participate in the oxidation reaction to produce CO2. Bimolecular rate constants for the reactions between these species and CO are also discussed.

Oct 1, 2003

By S. Ivanova

The results presented in this paper show that the gold solution dilution is a key parameter to control the dispersion of gold on ?-Al2O3 the selected support. The variation of concentration leads to changes in pH which modify the nature of gold complexes from HAuCl4 formed in the solution. These complexes are presented. Some of them (AuCl3(OH)- and AuCl2(OH)2 -) react with the surface of alumina and give interesting interaction. AuCl2(OH)2 complex has been considered as an ideal complex because of the strong anchorage of a bidentate species on the alumina. This complex is formed mainly in a solution of gold with a concentration of 10-4 M giving a pH of 3.5-4.5. The nature of the anchorage and the amount of chlorine, has an influence upon the formation of Au-Cl bridges which modify the dispersion of the gold on alumina of the final catalyst as shown by TEM.

Oct 1, 2003

By John A. Rumball, Martin R. Houchin

Data from autogenous and semi-autogenous tests in a 1.67m diameter mill have been analysed in terms of a new model for rock abrasion. This model defines specific rate as the rate of production of fines (material less than 13mm) per unit mass of rock, where the term “rock” is applied to all ore pieces of ore coarser than the grate size. In most cases, an allowance for preliminary rounding and cleavage was made. A method has been developed to analyse steady-state data, using piecewise fitting to the cumulative size distributions. The model was compared to the well-established models, which are based on the population balance method. The specific rate increased for all rock sizes as the volume of 100mm balls in the mill was increased. Tests using a coarser feed and smaller balls provided further evidence that once rocks are rounded, abrasion is due to localised surface damage, caused by impacts, rather than rotational shear. An allowance for rapid rounding of jagged rocks, followed by less rapid abrasion of rounded pebbles was also tested, but the analysis was not conclusive. The average specific rate is a useful measure of the capacity of a primary mill. The effect of power intensity (kW/t of ore) was also investigated as a means of extrapolating the pilot-plant data to large production mills.

Sep 29, 2003