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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 Antonio Laguna

During the past few years, synthetic efforts have been addressed to the synthesis of polymeric materials with optical or semiconducting properties or even with capabilities to act as sensors for volatile organic compounds (1). The most recent studies have been concerned with the synthesis of heterometallic systems with short metal-metal interactions and the determination of their optical properties. These complexes are undoubtly interesting from a theoretical viewpoint and include an emerging class of luminescent materials, in which the observed luminescence results mainly from the interactions among the different metal centers, as well as the environments of these atoms. The understanding of the photophysics and photochemistry of these products could permit the design of complexes with appropriate metals and ligands chosen for individual applications. Following a synthetic strategy consisting on reactions between acid heterometal complexes and basic gold precursors we have succeded in synthesizing supramolecular assemblies formed via acid-base stacking, which display tunable luminescence or selective and reversible sensitivity to Vapour Organic Compounds (VOC?s) (2-5). In this sense, in accord with previous Mössbauer studies carried out in the gold precursor complex [AuR2]- (R = C6F5), the basic properties of this and related materials have been employed as building blocks of supramolecular assemblies in their reactions with complexes in wich the metallic centers act as lewis acids as, for instance, Tl(I) or Ag(I) (6). For instance, in the case of silver, by reacting equimolecular quantities of [NBu4][Au(C6F5)2] with AgClO4, in acetone, a solid of stoichiometry [Au2Ag2(C6F5)4(OCMe2)2]n is obtained. The polymeric nature of this material in solid state is confirmed through X-ray analyses (figure 1). It consists of polymeric chains formed by repetition of Au2Ag2 moieties linked through short gold-gold interactions. Nevertheless, in solution, the nature of this polymeric materials was still a matter of controversy and, in this case, the optical properties have been shown as useful tools in order to obtain information. Thus, while dilute acetone solutions of this complex give a emission coming from pentafluorphenyl localized ??* excited states, in accord with the presence of isolated tetranuclear Au2Ag2 units, when the measurements are done at different and higher concentrations, a band that does not obey the Lambert-Beer law appears. This deviation is consistent with molecular aggregation in solution of these units through gold-gold interactions, and a clear correlation between the emssion wavelength and the structure in the solid state and in solution is shown (figure 2). DFT calculations accord with the observed experimental behaviour and show the nature of the orbitals involved in each transition.

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 Jef M. van der Zel

The idea of veneering rich yellow gold alloys with a low-melting, high expansion porcelain, has been a driving force for metal-ceramic research in dentistry. Since 1990, with the advent of the Carrara System (1), a low firing temperature veneering ceramic allowed the use of gold alloys with a lower content of platinum and palladium than the traditional gold-platinum ceramic alloys and thus a richer yellow color. The earlier high gold-platinum ceramic alloys contained at least 12 percent platinum group metals to allow for dimensional stability when firing the relatively high melting traditional ceramics. This amount of platinum group metals gave the alloys a greyish tinge which made them unattractively steel colored and difficult to present as ?high gold alloys?. In the 90?s the new generation universal low-melting, high expansion gold alloys gained market share at a steady rate, starting in Germany, and have now for a great part replaced the traditional gold-platinum alloys (Fig. 1). The first alloys contained 75 wt-% gold and up to 9 wt-% platinum or palladium. They provided a metal-ceramic system in which a gold alloy having an aesthetic yellow colour is fired on with a dental porcelain tailored thereto. The tailoring is meant in respect of compatible coefficients of thermal expansion, and compatible melting or softening points of metal and porcelain. The major concerns in the beginning were with thermal stability during firing, the thermal expansion coefficient of the alloy against the porcelain (compatibility) and the yellow color. In a later stage, alloys with gold contents in the range of 50-60 wt-% gold were developed in analogy with the pale yellow gold-reduced alloys that were formerly used for crown & bridge work and the white gold-reduced alloys used for metal veneering where gold was substituted in part by palladium.

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 Serena Biella

Gold has received a growing interest as a catalyst for the selective oxidation of organic molecules using oxygen under mild conditions1. In the liquid phase application small gold particles (2.5-7 nm) deposited over different solid supports can be used but, like many other noble metals, their catalytic activity depends upon the nature of the support and the preparation metod2-5. In particular, gold on carbon is the preferred catalyst for the oxidation of the alcoholic 2-7 and the aldehydic7-9 groups and one of the best preparation method is the immobilisation of colloidal particles2-5,8,9. Suggested application of gold catalysis in fine chemicals production, tested on laboratory scale preparations, is reported in table 110. In order to produce more efficient catalysts for the liquid phase oxidation and to derive new insights into the reaction mechanism, we have made a comparison among catalytic systems based on different metals. The first effort was to test the activity, if present, of naked metal particles and then to study the influence of various materials commonly used as a support.

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 Michio Okada

Dissociative adsorption of hydrogen (deuterium) on thin gold films grown on Ir{111} surface has been studied with temperature-programmed desorption using a quadrupole mass spectrometer and nuclear reaction analysis. Thin Au{111} films are epitaxially grown on Ir{111}. Surprisingly, H2 (D2) can dissociatively adsorb on these Au{111} films, although it is well known that Au surfaces are noble enough not to dissociate hydrogen molecules [B. Hammer and J.K. Nørskov, Nature 376, (1995) 238]. We attribute this to the sensitivity of hydrogen to changes in the local surface properties, e.g., electron localization (the narrowing of the s-band, the s-band center model), which could explain the upto now unexpected high for the reactivity of a thin Au{111} surface. Moreover, we found that H (D) atoms can be confined into a Au thin film and/or the interface between an Ir surface and the thin Au film. We demonstrate how anomalously reactive thin Au films grown on an Ir surface are, and also compare the Au films with Ag films grown on Ir to test the validity/generality of our proposed s-band center model.

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 Andreea Catalina Gluhoi

Oxidation and reduction reactions of N-containing molecules have been studied over different types of gold-based catalysts, Au/MOx/Al2O3 and Au/MIOx/MIIOx/Al2O3 (M, MI, MII=Li, Rb, Mg, Ce, Zr, Mn, Cu) prepared by deposition precipitation with urea. In general, all the catalysts were already active at low temperatures. NH3 oxidation was effectively catalyzed by Au/CuO/Al2O3, a catalyst which also gives the highest yield in N2. NO reduction by H2 performed over gold-based catalysts produced N2O, N2 and NH3 and N2O reduction resulted in the formation of dinitrogen. For all the reactions, large synergistic effects have been obtained by addition of different kind of additives.

Oct 1, 2003

By Masaru Kato

The plated gold being used by the electronics industry can be broadly classified into two categories: soft gold and hard gold. Soft gold is used for circuit metallization and for bonding semiconductor chips, while hard gold is indispensable as the contact material on electrical connectors, electromechanical relays, and printed circuit boards. The traditional baths from which to plate soft gold as well as hard gold contain the cyanide complex, [Au(CN)2]-, as the source of gold, which liberates free cyanide ions during the plating. The free cyanide is not only highly toxic but also attacks photoresists used to delineate circuit patterns and bonding pads. For these reasons, non-cyanide baths are in use to plate soft gold, whereas hard gold can be plated only from cyanide baths at present. In this presentation, the current status of both electrolytic and electroless non-cyanide processes for plating soft gold will be reviewed.

Oct 1, 2003

By Eamonn F. Maher

Superconductivity is one of the most remarkable scientific phenomena ever investigated. It is the phenomenon whereby some materials exhibit zero resistance to the passage of an electric current when cooled to low temperatures, and requires a quantum mechanical explanation. Four Nobel prizes in physics have been awarded specifically on the subject of superconductivity, with many more enabled by superconducting technology. For example, particle beams are generated in accelerators and manipulated in ?particle beam lines? in the ?Big Physics? projects around the world eg. at CERN, Geneva, leading to major discoveries in fundamental particle physics. Similarly, at the JET Propulsion laboratory near Oxford, U.K, controlled nuclear fusion has been demonstrated, and magnetic containment of plasmas is key. In the chemical and biological sciences high field NMR spectroscopy has become indispensable for examining organic matter, revealing the mysteries of the workings of cells, genetics, and in the development of new polymers and pharmaceuticals. With all these very advanced uses for superconducting magnets, it is easy to forget that superconductivity is big business, not just a scientific curiosity. MRI (Magnetic Resonance Imaging) superconducting magnets, the key component of high resolution body scanners, use approximately half of the world?s superconducting wire ? the other half being mostly used in accelerator magnets. The MRI market is about 3 billion dollars per annum, and one MRI magnet uses 200km of wire. New applications for superconducting magnets are now appearing including ?Catheter steering?, enabling much shorter timescales for life-saving brain tumour removals and ?Functional MRI?, a whole new area in patient diagnostics. Whilst the use of low temperature superconductors (LTS) is now well established commercially in superconducting magnets and niche electronic applications, the application of LTS in electric power distribution and transport has been very limited to date. It is now more than fifteen years since the so-called High Temperature Superconductor (HTS) materials were discovered: these can be operated at liquid nitrogen temperatures rather than liquid helium temperatures. However, materials processing and scale-up issues have prevented their widespread use, and in particular the required price/performance criteria are only beginning to be reached except in certain niche markets. BSCCO (Bismuth Strontium Calcium Copper Oxide) tapes up to one km long are now readily available, and have been demonstrated in high current cables for power distribution networks, but the general consensus is that 1) it is difficult to reduce the price much further because of the silver matrix required and 2) in applications where coils are required eg. motors, generators, transformers etc the properties of BSCCO are rather poor because of the critical current dependence on magnetic field. Magnetic fields are always associated with coils and windings, and such fields are of course fundamental to the operation of all electrical machines. YBCO (Yttrium Barium Copper Oxide) however, has good characteristics in field and for the last few years there has been intensive research and development costing several tens of millions of dollars worldwide into the scale-up of production of so-called ?coated conductor?. This ?second generation? tape can be produced by any of many different film deposition techniques, with more or less success for short lengths, but as yet it is unavailable in lengths more than a few tens of metres.

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 Timothy W. Ellis

Gold-based materials have been a mainstay of the electronics and semiconductor industry since the physics was just a laboratory curiosity. Gold is the workhorse material in wire bond, flip chip and off wafer interconnections due to its corrosion resistance, ability to form metallurgical bonds by soldering or cold welding, and ease of fabrication. As the electronics and semiconductor industries grew, so did the use, of Gold in spite of the feature size reduction so elegantly demonstrated in Moore?s law. However, several revolutions in the Silicon miracle are threatening Gold?s place as the material of choice. Although cost is always an issue, the limitations are associated with the chemistry of Gold based alloys. Will Gold remain? Emerging requirements of bioelectronics, photonics and power requirements in conventional device represent new opportunities for Gold to shine. Additionally, as the world market demand for electronic, semiconducting, bio-electronic and photonic technology increases, given the right technology, Gold still can provide value proposition.

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