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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'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 Yongbao Zhu

The Ag2O-mediated reactions of cycloaurated compounds with a general formula Au(L)Cl2 (L = bi-dentate C?N ligand) with thiosalicylic acid, N-acetyl cysteine or 1,2-benzenedithiol in DMF proceeds via ligand substitution of the Au?Cl bonds to afford the S-O and S?S adducts all in good yields. The reactivity of the dichloro, S-O and S-S adducts towards thiols were examined by reacting with cysteine in an aqueous medium, revealing that all of Au-Cl, Au-O and Au-N are labile for thiol displacement. The measurement of the inhibitive activities of these compounds against human cathepsins B and K showed that the dichloro and S-O adducts are effective inhibitors with IC50 values ranging from 0.1 to 2.6 -M, and that the S-S adducts are inactive.

Oct 1, 2003

By Daniel B. Leznoff

The cyanoaurate anions [Au(CN)2]- and [Au(CN)4]- are shown to be useful building blocks for synthesizing supramolecular coordination polymers. For the gold(I) unit, aurophilic interactions often increase the structural dimensionality of the system and can impart increased thermal stability to the metal-polymers produced. A series of polymers of the form M[Au(CN)2]2(Ligand)x have also been prepared and show large colour changes upon changing the ligand, thus illustrating a sensor-type application. Both building blocks can mediate significant antiferromagnetic and ferromagnetic interactions between transition-metal centres in the polymers. For the gold(III) unit, no metal-metal interactions are observed, although weak Au-N(cyano) interactions control the intermolecular packing. Several structural examples of cyanoaurate-based coordination polymers are presented, including 2-D and 3-D arrays and a supramolecular square.

Oct 1, 2003

By Ana Adé

The use of gold compounds in homogeneous catalysed organic reactions has been undervalued for many years due to the preconceived opinion that gold is an expensive and extremely chemically inert metal. However, recent reports have changed this assessment and gold salts in small amounts are known to display high catalytic activity.[1] Thus, it has been reported recently that anhydrous AuCl3 catalyses the formation of C-C and C-O bonds (usually mediated by hydrochloric and other protonic and Lewis acids).[2] Some examples include Michael type additions, selective cross cycloisomerisation/dimerisation of propargyl or allenyl ketones, benzannulation between o-alkynylbenzaldehides and alkynes or cyclisation of alkenyl furans. It is noteworthy that some of these reactions[2a] can be also catalysed by silver salts but with much lower yields. The 1,3-dipolar cycloaddition of nitrones to alkenes is a powerful synthetic method that has found numerous applications in the synthesis of a variety of carbon frameworks.[3] Several laboratories have focused on the development of Lewis acidic reagents to modulate the selectivity of the reaction.[4] Despite the extensive study performed, there are not many examples in which a metallic complex catalyses the dipolar cycloaddition. Most of these reactions require the presence of a metallic complex and nitrone in a 1:1 molar ratio. Recently, we have carried out stoichiometric reactions of the N-benzil-C(2-pyridil)nitrone, 1, with different dipolarophiles in the presence of zinc and silver compounds.[5] Apart from an increase of the reaction rate and the selective formation of one of the possible isomers, we have shown the formation of zinc and silver-nitrone complexes during the reaction, which behave as the intermediates in the cycloaddition process. As suggested by the results obtained with silver complexes, we decided to test gold derivatives (in the oxidation states of I and III). Interestingly, we have found that they can be used not only as stoichiometric reagents but they can also mediate these cycloadditions in catalytic amounts (5 to 10 mol % respect to the nitrone). Here we present the results on the 1,3-dipolar cycloaddition reaction of the N-benzil-C(2-pyridil)nitrone (2-PyBN), 1, and methylacrilate, 2, (Eq. 1) catalysed by gold(III) derivatives.

Oct 1, 2003

By Shamil Shaikhutdinov

CO adsorption on gold particles deposited on well-ordered alumina and various iron oxide films has been studied with temperature programmed desorption (TPD) and infrared reflection adsorption spectroscopy (IRAS). Structural characterization has been performed with scanning tunneling microscopy. Data show that the CO adsorption exhibits a size effect in that small particles adsorb CO more strongly. The effect generally vanishes after annealing to 500 K. For annealed samples, CO TPD and IRAS spectra are nearly independent of the particle size and supports studied. The results indicate that the CO interaction with gold surfaces is essentially similar and involves low coordinated atoms.

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 Christopher W. N. Anderson

Induced hyperaccumulation of gold by plants was first reported in 1998 by researchers from Massey University in New Zealand who proposed the idea of mining gold using plants (phytomining). Since that time research has been conducted to understand the conditions under which plants can be made to take up economic amounts of the metal. One key focus has been on the geochemistry of gold-rich soils, leading to a diagnostic test that can predict how suitable a particular soil might be to gold phytomining. Field trials have been conducted at several locations around the world in collaboration with industry partners. A Decision Support System has been developed to assist in the design and management of phytomining operations, and economic modeling has been carried out to set targets levels for phytomining technology. Novel studies are now examining the form of gold in plants. Research suggests that plants may store gold as discrete metallic nanoparticles in leaf and stem tissues, an observation that may lead to new ways to recover the metal from harvested biomass.

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 Jeremy D. Glennon

A number of exciting challenges, opportunities and unanswered questions remain concerning the chemistry, geochemistry, medical, industrial and analytical applications of gold and its compounds.1 Among the challenges presented is the need for extraction methods for gold, at process and indeed analytical scales, that avoid the use of organic solvents or hazardous reagents. Extensive environmental contamination has occurred in the Brazilian Amazon from the mercury-gold amalgamation process. Major problems with the cyanidation process are the relatively slow dissolution kinetics and the health and environmental problems associated with it. With innovation and technical changes, a cleaner way for solubilising and extracting this versatile precious metal can be found. This cleaner future may lie in supercritical fluid science. Interestingly, geochemical studies of gold solubility and speciation in hydrothermal solutions have highlighted the importance of supercritical conditions and sulphur species in the deposition of gold in natural environments. Gold solubility in supercritical brines is far higher than previously supposed while interest in the high content of carbon dioxide in the mineralizing fluids is growing. 2,3 In recent years, also, there has been a tremendous amount of attention paid in analytical chemistry and in industry, to the area of supercritical fluid extraction (SFE) of organic and metallic species. 4 This interest has been fuelled by the introduction of more stringent environmental control and the subsequent need for cleaner solvents and processes to replace established ones. Carbon dioxide is the substance of choice for SFE because of its moderate critical parameters (Tc = 31oC, Pc = 73atm), inertness and availability in pure form. It is an excellent extraction medium for non-polar and moderately polar species, and with careful ligand design, it can be used for analytical and process scale metal extraction from solution and solid phases. In general, the dissolution of a metal in supercritical CO2 (sc-CO2) requires that the charge on the metal ion be neutralised on complexation by the ligand or through a form of ion pairing (analogous to the situation where metal ions are extracted into organic solvents, such as methyl isobutyl ketone or toluene). In this way, then, many chelating agents such as dithiocarbamates and hydroxamic acids have been utilised to extract metal ions such as Cu and Fe into sc- CO2, the process greatly enhanced by the use of fluorinated ligand derivatives. 5-7 In this review paper, we show that supercritical conditions and complexation with sulphur donor atoms, important in the natural deposition of gold, can form the basis of a clean, eco-friendly chemistry for gold extraction. Analytical scale extractions of gold from a variety of matrices can be conveniently used to assess the efficiency of any new proposed ligand.

Oct 1, 2003

By Donald S. Cameron

By dispersing gold in high surface area form supported on metal oxides, its inert character can be transformed to make economical, effective catalysts. Gold has already been demonstrated in a number of fuel cell applications such as gas phase catalysts, electro-catalysts, and electrical connectors. In this paper, the various types of fuel cell systems are reviewed, and several opportunities for gold identified. Low temperature fuel cells, including alkaline and solid polymer electrolyte types rely on high surface area platinum group metal catalysts which are highly susceptible to poisoning by low concentrations of carbon monoxide in the fuel supply. Hydrogen is frequently obtained by steam reforming hydrocarbons, followed by the water gas shift (WGS) reaction. A promising initial use for supported gold catalysts is in catalysing this WGS reaction. Research has shown that gold supported on iron oxide (Au/a-Fe2O3 ) WGS catalysts are more active than the current commercial copper oxide / zinc oxide catalysts, and effective at temperatures as low as 120oC. Products from reformer/ water gas shift reactors can be further purified by removing traces of carbon monoxide. If a small proportion of oxygen is introduced into the fuel gas stream, carbon monoxide can be preferentially oxidized to carbon dioxide even in the presence of hydrogen. Gold nanoparticle catalysts on iron oxide support (Au/a-Fe2O3 ) have exhibited higher activity than commercially available platinum on alumina (Pt/?- Al2O3 ) preferential oxidation catalysts. The low temperature of this reaction may make it feasible to incorporate these catalysts within the fuel cell itself. Proton exchange fuel cells provide several possible applications for catalytically active gold and its alloys. Carbon supported platinum group metals would benefit greatly from improved electrical conductivity if gold replaced some or all of the carbon support material. As electrode current densities are raised, electrical resistance constitutes an increasing proportion of voltage losses within the fuel cell. Dramatic reductions in cell stack voltage losses have already been demonstrated by reducing inter-cell contact resistance using gold plating. The low temperature oxidation properties of gold catalysts have been investigated in controlling gaseous emissions from direct methanol fuel cells, and gold also provides essential catalysis in building direct borohydride oxidation fuel cells. The prospect of a range of other applications for gold in fuel cells to contribute useful improvements in corrosion resistance and conductivity is assessed. Globally, fuel cells have been developed for a wide range of applications including stationary generators, cars and buses, industrial vehicles and small portable power supplies, each of which represents a substantial market. Hence there are likely to be many and varied opportunities for gold catalysts to contribute to the performance and economics of the systems being commercialized.

Oct 1, 2003

By Masakazu Daté

Moisture effect has been studied for the CO oxidation over Au/TiO2, Au/Al2O3 and Au/SiO2, in the range of H2O concentration over four orders of magnitude. It has been found that the catalytic activity is generally enhanced by moisture in the reactant gas. The enhancement is as large as two orders of magnitude. Response to the moisture concentration, however, depends on the support oxide, indicating different contributions of the support to the reaction steps. The moisture effect is reversible and the activity is mainly determined by the amount of moisture absorbed by the catalyst. The apparent activation energies are not significantly influenced by moisture for Au/TiO2 and Au/Al2O3. On the contrary, non-uniform conversion curves versus temperature observed for Au/SiO2 are drastically changed, which indicates that the reaction over Au/SiO2 does not take place at low temperatures without moisture. The moisture effect may be probably attributed to the decomposition of carbonate species accumulated during the reaction, while the ?OH group might directly participate in the reaction pathways as a promoter.

Oct 1, 2003

By Candido Bariáin

A new vapochromic material of formula [Au2Ag2(C6F5)4(bipy)2]n (bipy = 2,2´ bipyridine) has been developed and used for the detection of some volatile organic compounds as acetone either in vapour or in water solution. The material is presented in the form of powders which colour changes with acetone vapours turning from bright yellow in the absence of vapour to white in the presence of vapour. By using the sol-gel technique, the powder ? dispersed in tetraethyl orthosilicate- was easily deposited on optical fibres. In order to study experimentally the behaviour of this material for construction practical optical fibre sensors, a sol-gel material doped with the vapochromic material is deposited onto an extreme of a monomode fibre connected to a coupler. The behaviour of the material was studied for different wavelengths and concentrations of acetone vapours and acetone/water solutions. Changes up to 4dB in the reflected optical power were detected. Optical fibre sensors have many advantages over conventional ones, such as electromagnetic interference immunity, passivity behaviour, possibility of using multiplexation techniques, low weigh and little size, etc. Actually, there is an increasing interest in developing optical fibre sensor for vapour detection in the chemical industry and in fact many sensor had been developed [1]. Some are based on the deposition of a sol-gel-based material either over the core of an optical fibre [1] or onto the thinner zone of a biconically tapered optical fibre [2]. Others are based on Fabry-Perot interferometers [3]. Also there are sensors based on the reflection of the light on films, on the fluorescence of dye-doped polymer cladding in fibre, on colorimetric reagents in the core of a silica fibre or on surface plasmon [4]. The possible materials for the construction of such sensor should be colorimetric reagents able to change the colour or refractive index in the presence of same organic vapours. There are not many metallic complexes with these properties, although same interesting examples have been reported in the chemistry of palladium and platinum as [Pt(p-R-C6H4NC)4][Pd(CN)4] described by Nagel [5] and Mann [6], which reported the construction of some LEDs. We recently reported the preparation of a novel vapochromic material (Fig 1) [7] which can be used for the construction of optical fibre tapered environmental sensors [8,9] of vapour organic compounds (VOC´s). Also we reported other nickel and palladium derivatives which present this type of behaviour [10]

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

By Alfredo Cámac Torres

El presente texto refiere el uso de la filosofía JAT (justo a tiempo) en los procesos de producción y calidad total de la minería. El sistema JAT se presenta como un enfoque de organización de gestión en la industria minera, cuyo objetivo es el mejoramiento continuo y la eliminación de pérdidas en las actividades internas y externas que sean diferentes de los recursos mínimos absolutos como son los equipos y maquinarias, materiales, insumos, mano de obra, y otros que pueden incrementar el costo de producción.

Jul 31, 2003

By William Arenas

"De acuerdo a la evaluación geotécnica realizada en las galerías permanentes de los cuadros de soporte de la mina Ares, se observó que dichas estructuras sufren roturas o deformaciones con el tiempo, generando una alza de costos e inseguridad para las labores del personal. En ese sentido, el presente trabajo señala la aplicación de nuevas tecnologías de sostenimiento en la mina Ares tales como el uso de segmentos metálicos o cimbrasen las galerías de avance y preparación o el túnel liner -en tanto, el primero soporta grandes presiones y se puede reutilizar, mientras que el segundo, es un mecanismo que otorga confianza al trabajador durante su tránsito, de forma que evita el ingreso de agua en demasía a la galería, derivándola hacia el relleno o estructura. En consecuencia, se sugiere la colocación de túnel liner o túnel ovoide (en proyecto), en las minas que tengan características geomecánicas similares a las de Ares."

Jul 31, 2003

By Víctor Romero

Anteriormente el método que se utilizaba para la separación de cobre y plomo en la mineralización a través del depresante bicromato no logró obtener la concentración adecuada en la planta de Raura. En ese sentido, el presente trabajo describe el uso del depresante de plomo denominado RPB, cuyo compuesto de bicromato con Carboxy metilcelulosa (CMC) y fosfato de sodio, es el más adecuado para ser aplicado en la planta Raura, así como en otras minas.

Jul 31, 2003