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•Platinum Metals Rev., 2010, 54, (2), 130–132• CATALYSIS – APPLIED AND PHYSICAL CATALYSIS – REACTIONS
Surfactant- and Polymer-FFree Col oidal Platinum Krka, dd, Novo mesto, World Appl. 2010/003,942 Tanaka Kikinzoku Kogyo KK, Japanese Appl. 2009-228,067 Enantiomerically-enriched alcohol precursors for A stable colloidal solution with 300–20,000 ppm Pt duloxetine are prepared via asymmetric transfer which can be used in catalyst preparation is produced hydrogenation (ATH) of β-keto amines with an without the need for a protective agent. A Pt salt such optionally protected amino group. The catalyst is a as Pt(NH3)2(NO2)2 is dissolved in water or water and chiral Ru or Rh (preferably Ru) complex prepared an organic solvent, and NaOH and/or NaHCO3 is from a metal source such as [RuCl2(p-cymene)]2 and added to adjust the pH to 7.0–8.5. An inert gas is bub- a chiral ligand such as (S,S)-Me2NSO2-1,2-diphenyleth- bled through the solution to lower dissolved O2 to <1.0 ylenediamine, which is preferably of >99% enan- ppm. The Pt salt is then reduced to Pt metal particles, tiomeric purity. The ATH can be carried out in a preferably using EtOH, at 80--92ºC. Ultrafiltration of the solvent at 0–70ºC, in the presence of one or more H reduced solution adjusts electrical conductivity to donors such as 2-propanol or formic acid. Resulting <100 mS m–1 and pH to 7.0–12.0, and the pH may be product enantiomeric and chemical purities are >98%.
EMISSIONS CONTROL
CATALYSIS – INDUSTRIAL PROCESS
Rhodium-CCatalysed Synthesis of Lactic Acid Esters Toyota Jidosha KK, World Appl. 2010/001,226 Uhde GmbH, European Appl. 2,141,145; 2010 A TWC has two catalyst layers deposited on a chan- A process for the synthesis of enantiopure lactic acid neled substrate. The lower layer has 0.25--5.0 g l–1 of esters is claimed. Asymmetric hydrogenation of each of Pt and/or Pd, with Pd deposited upstream of prochiral α-acetoxy acrylic acid esters in the pres- Pt and forming 20–45% of the length if present.As the ence of 0.1–2 mol% Rh-based catalyst and in a solvent exhaust gas first contacts Pd, Pt is exposed to cooler such as propylene carbonate is carried out in an and less oxidising conditions and thermal deteriora- autoclave at 20–40ºC under H2 pressure of 1–20 bar.
tion is minimised.The upper layer has 0.1–1.2 g l–1 Rh The catalyst or precatalyst is a Rh–bisphospholane and is 10–50% shorter than the lower layer so that complex such as [Rh(L)(1,5-cyclooctadiene)]BF4 or both layers are exposed to the exhaust gas for opti- [Rh(L)(norbornadiene)]BF4 where the ligands L are mal conversion, while Rh and Pt are kept separate to heterocyclic phosphines which may be selected from: BASPHOS, binaphane, one of the DuPhos family E. M. Cunningham, US Appl. 2009/0,298,674 Natl. Inst. Adv. Ind. Sci. Technol., Japanese Appl. An additive to promote more efficient hydrocarbon oxidation in an internal combustion engine consists A method for the production of biogas from waste of: (a) a Pt compound, specifically bis(2,4-pentane- paper such as shredded paper that is unsuitable for dionato)Pt; (b) a Pd compound, specifically bis(2,4- recycling is claimed. Water and paper in a mass ratio pentanedionato)Pd; (c) a Fe compound such as fer- of between 1–100 are heated to 200–450ºC in the pres- rocene; (d) a Mg compound such as Mg 2-ethylhexa- ence of a catalyst such as 5 wt% Ru on activated car- noate; and (e) a Re- or Ce-containing carboxylate, in bon. A typical batch reaction at the laboratory scale a liquid medium, specifically aromatic hydrocarbon gives cellulose conversion efficiency of 100% and 150. Pt and Pd are each present in amounts yields fuel gas consisting of 48% CO2, 47% CH4, 5% H2 ~100–2000 ppm. It may either be independently delivered to the engine or added to the fuel.
•Platinum Metals Rev., 2010, 54, (2)• FUEL CELLS
anode gas of a fuel cell. It may also be used to regen- erate a Pt catalyst which has been deactivated through CO poisoning, or in the sensor of a CO detector.
AMOMEDI Co, Ltd, World Appl. 2010/010,990 An electrode for a fuel cell is claimed, in which the Pt catalyst layer and the gas diffusion layer are inte- METALLURGY AND MATERIALS
grated for improved efficiency. A nanofibre web, preferably 300–1000 µm thick with fibre diameter Iowa State Univ. Res. Found., Inc, US Appl. 2009/0,324,993 <1 µm, is formed by electrically spinning a solution A pgm-containing alloy for use in bulk form or as a of a carbon fibre precursor such as cellulose and is coating on gas turbine components is claimed. It con- then oxidised and carbonised, and may include sists of: ~3–20 at% of one or a mixture of Pt, Pd, Rh or nanomaterials such as carbon nanotubes. The web is Ru; <23 at% Al, where this amount can be limited as a treated with a water-repellant fluorine-based resin, function of the concentrations of Ni and pgm so that either on one or both sides, and has a final resistivity no β-Ni-Al phase is formed; at least one reactive ele- of <11.5 mΩ cm2. A Pt-based catalyst is deposited ment such as Hf, Y, Zr, La, Ce, preferably including Hf directly on the web, using a method such as vacuum and in an amount 0.5–1 at% (or up to 2 at% if Si is present); and the balance Ni. It may also include 3–20 at% Cr, preferably 5–15 at%, and/or 7 at% Si. Al and Ni are present in the γ' phase.
Natl. Inst. Adv. Ind. Sci. Technol., Japanese Appl.
2009-214,092 The Rh complex 1,which may be supported on a con- Citizen Holdings Co Ltd, Japanese Appl. 2009-221,536 ductive carrier such as carbon black, is claimed as a A jewellery alloy is described as having high hardness catalyst for electrochemical oxidation of CO.The com- for scratch resistance while maintaining the charac- plex can be used in the anode of a CO-fuelled PEMFC, teristic appearance of pure Pt. The Pt alloy is formed or may be included in a device to remove CO from the by first adding ≤2.0% B to ≥98.0% Pd (by weight) toobtain a uniform Pd-B alloy, then: (a) dissolving ≤5.0% of this PdB alloy in ≥95.0% Pt; or (b) dissolving ≤0.5%of the PdB alloy and <1.0% of one or more of Nb, Ta, APPARATUS AND TECHNIQUE
Flange for Direct Resistance Heating of Platinum Corning Inc, World Appl. 2009/108,314 A disc-shaped flange for heating a vessel carrying molten glass consists of concentric rings. The inner rings are composed of a similar high-temperature Pt alloy (>80% Pt, e.g. 10RhPt) to that of the exterior wall R1– R8 may be selected independently from: of the vessel, to which the innermost ring of the flange is welded. The outer rings are composed of >99% Ni alloy and receive electric current from a bus bar. Heating occurs as current flows through the Pt- containing rings, which are constructed to minimise heat loss through the flange and ensure optimal heat- ing of the vessel wall. An intermediate ring of Pt-Ni alloy with >77% Pt may also be included.
•Platinum Metals Rev., 2010, 54, (2)• rination of organic compounds through the transfer Los Alamos Natl. Secur. LLC, US Patent 7,611,565; 2009 of electrophilic F+, such as in the reaction with aPd(II) aryl complex to yield a fluorinated aryl com- A device for H2 separation incorporates a thin, uni- pound, and can specifically be applied in the prepa- form Pd or Pd alloy membrane deposited on a ration of 18F- or 19F-labelled imaging agents for porous support consisting of spherical microparti- cles, formed preferably of (in wt%) Fe82Al16Cr2 andcoated with an atomic diffusion layer of Al2O3 that is substantially incapable of H ELECTRICAL AND ELECTRONICS
of the support are sized 0.05–0.5 µm, preferably Deposition of Iridium Film on a Memory Capacitor 0.1--0.3 µm,and sintering at 975ºC for 4 h may be used Tosoh Corp., Japanese Appl. 2009-235,439 to achieve a narrower pore size range.
A uniform thin film of Ir and/or Ir oxide is formed on BIOMEDICAL AND DENTAL
a three-dimensional structure by spraying a solutionof an Ir complex such as [Ir(ethylcyclopentadienyl)- Novel Route to Platinum Anticancer Compounds (1,3-cyclohexadiene)] in a solvent such as EtOH onto Johnson Matthey Plc, World Appl. 2009/150,448 a semiconductor substrate heated to just above thedecomposition temperature of the Ir complex.
X[PtCl3(NH3)] where X is an alkali metal ion,preferably K+, is produced via the intermediate(NBu ELECTROCHEMISTRY
4)[PtCl3(NH3)] and can be used in the synthesis of Pt anticancer compounds, specifically cis- [PtCl2(NH3)(2-picoline)]. A mixture of cisplatin, con- Phelps Dodge Corp., US Appl. 2009/0,288,856 centrated HCl, NBu4OH(aq), saturated NaCl(aq) and aPt catalyst, specifically Pt black, in an organic solvent An anode for electrowinning consists of IrO2 or a such as chlorobenzene is heated, preferably at reflux, mixture of ~80 mol% IrO2 and ~20 mol% Ta2O5 coated on a conductive substrate such as Ti. Two layers are the mixture and concentrated before being reacted present: the first has IrO2 in the crystalline phase, with an alkali metal salt in an alcohol. For example, formed by heating a solution of a suitable precursor reaction with KOAc in EtOH yields 50–60% to between 450–550ºC; the second has amorphous 2, formed by heating the precursor to between 340–430ºC. The coating is described as potentially CHEMISTRY
improving process efficiency of Cu electrowinningoperations by reducing cell voltage by ~15%.
Pal adium(IV) Fluoride ComplexesPres. Fell. Harvard College, World Appl. 2009/149,347 PHOTOCONVERSION
High-valent Pd–F complexes, typically Pd(IV)–F com-plexes such as 1, which are stabilised by the inclusion of two fixed multidentate ligands,and their method of University of Utah, US Appl. 2009/0,313,891 preparation are claimed.They are applied in the fluo- Polymers with a π-conjugated backbone containingPt or Ir atoms and emitting phosphorescence and flu-orescence at approximately equal levels are claimed.
They are formed for example by incorporation of Pt atoms into bis-1,4[2-(4-ethylphenyl)ethynyl]benzene from selected amounts of a complex such as PtCl2(PBu3)2. The polymers can be tuned to emit required levels of both blue-green and red visible light by varying the spacing of monomers carrying Pt or Ir atoms, and they are particularly suited to plant-

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