Journal Archive

Platinum Metals Rev., 2012, 56, (4), 281
doi: 10.1595/147106712X656662

Patents: October 2012


Carbon Supported Palladium Catalyst

Université Catholique de Louvain, European Appl. 2,468,701; 2012

The Suzuki-Miyaura C–C coupling reaction here consists of an aryl halide reacting with an arylboronic acid in an organic solvent in the presence of a Pd/C catalyst (the specific surface area of the C support is ~100 m2 g−1) and an inorganic base selected from K2CO3, NaOH, KOH, Na2CO3 or NaHCO3. The reaction is carried out at constant pH, preferably pH ~10.6.

Ruthenium-Carbene Complexes

BASF SE, US Appl. 2012/0,165,588

A Ru-carbene complex, 1, supported on SiO2 is used in olefin metathesis for the preparation of cycloalkadienes from cycloalkene monomers, polycycloalkenylenes or a combination of these in a continuously operated reactor. X1 and X2 can either be identical or different and are each an anionic ligand; L1, L2 and L3 are each an uncharged electron donor ligand; T is O, S, NR or PR; R is H or a C1–C40 radical; R1 and R2 are H, a C1–C40 radical or two or more ligands or radicals selected from X1, X2, L1, L2 and L3 and may be joined to one another to form a cyclic or polycyclic ring system; k is 0 or 1; n is 0 or 1 and m is 0, 1 or 2.


Manufacture of Vinyl Chloride

Solvay SA, World Appl. 2012/084,643

Vinyl chloride is manufactured by reacting C2H2 with HCl, using a catalytic system comprising of an N-alkylated imidazole selected from 1-methylimidazole, 1-ethylimidazole, 1-butylimidazole, 1-hexylimidazole, 1-octylimidazole, 1-decylimidazole, 1-methyl-2-octylimidazole, 1-ethyl-2-methylimidazole, 1-butyl-2-methylimidazole, 1-hexyl-2-methylimidazole and 1-decyl-2-methylimidazole and a compound of a metal chosen from Pt, Pd, Os, Ru, Au and Hg, preferably Pd, for example, PdCl2. The reaction is carried out between room temperature and 220°C.


Saccharification of Biomass Materials

Tanaka Noble Metal Industrial Co, Ltd, Japanese Appl. 2012-110,873

The saccharification of biomass materials is catalysed by Ru or Pd catalyst supported by cellulose carbonisation products containing 2.4–7.0 wt% SO3H groups. The cellulose carbonisation products have a degree of crystallinity of 1.8–2.4. The catalyst is manufactured by carbonisation of cellulose powder at 400–900°C for 1–10 h, immersion of the resulting supports in a solution containing Ru and/or Pd, then heating in concentrated H2SO4 or fuming H2SO4 for the binding of the SO3H groups to the supports. Cellulose was saccharified using a Ru catalyst supported on carbonised cellulose containing SO3H groups at 230°C for 1 min to give glucose in 40% yield and 68% cellulose conversion.

Hydrogenation of Vegetable Oil

Russian Federation represented by the Ministry of Industry and Trade of the Russian Federation, Russian Patent 2,452,563; 2012

A Pd-containing catalyst is used in the hydrogenation of vegetable oils resulting in a reduced content of trans-isomers. The catalyst consists of crystallites of catalytically active Pd applied over a C carrier surface with a granule size of 1.0–5.0 nm, specific surface area of 100–450 m2 g−1 and a mean pore size of ≥4 nm.


Lean-Burn Engine Oxidation Catalyst

Johnson Matthey Plc, World Appl. 2012/085,572

An exhaust system consists of a first oxidation catalyst containing Pt or Pt-Pd supported on a reducible oxide selected from Mn, Fe, Sn, Cu, Co, Ce or optionally a stabilised homologue of one of these disposed on a first honeycomb monolith substrate. The loading of the pgm on the monolith substrate is >10 g ft−3. The first oxidation catalyst may comprise of a molecular sieve which consists of Cu and/or Fe and at least one precious metal.


Oxygen Evolution Catalyst

Johnson Matthey Plc, World Appl. 2012/080,726

A catalyst layer for a fuel cell consists of an electrocatalyst and a crystalline metal oxide oxygen evolution catalyst. The oxygen evolution catalyst comprises of: (a) one or more metals selected from the lanthanides, Y, Mg, Ca, Sr, Ba, Na, K, In, Tl, Sn, Pb, Sb and Bi; (b) one or more metals selected from Ru, Ir, Os and Rh; and (c) O. The atomic ratio of the first metal(s) to the second metal(s) is from 1:1.5 to 1.5:1 and the atomic ratio of (first metal(s) + second metal(s)):oxygen is from 1:1 to 1:2. The formula of the oxygen evolution catalyst is (AA´)a(BB´)bOc where A and A´ are selected from group (a); B is selected from group (b); B´ is selected from (b), or from Ca, Mg or rare earth metals; a = 0.66–4.5; b = 1–3; and c = 3–11.

Palladium/Carbon Oxidation Electrode

Hitachi Ltd, European Appl. 2,469,632; 2012

The MEA for a fuel cell comprises an anode containing a catalyst selected from Pt, Ru, Ir, Rh, Os, W, Mo, Fe, Co, Ni or Mn, a solid PEM and a cathode. An additional HCOOH oxidation electrode containing Pd/C and a solid polymer electrolyte is formed between the anode GDL and the anode and between the cathode GDL and the cathode.

Platinum Alloy Catalyst with Conductive Polymer Coating

Hyundai Motor Co, US Appl. 2012/0,135,137

A Pt catalyst on a C support selected from C black, C nanotubes, C nanofibres, C nanocoils and C nanocages is prepared by coating the surface of the Pt catalyst with either polypyrrole or polyaniline. A transition metal salt selected from nitrates, sulfates, acetates, chlorides or oxides of Pd, Ru, Co, Fe, Ni, Ti, V or Cr is supported on the coated catalyst and this is heat treated at 700–1000°C.


Palladium-Based Metallic Glasses

California Institute of Technology, US Appl. 2012/0,168,037

A metallic glass free from Ni and Cu consists of a biocompatible alloy represented by the formula: PdaXbSicPdGee where X is Ag, Au or a combination of both; a (in at%) = ~74–86; b = ~2–5; c = ~8–10; d = 4–8; and e = ~0–3. This may be used to form a 3D object and be used in biomedical components such as dental or orthodontic components, implant or fixation devices or in jewellery applications.


Analyte Sensor

Abbott Diabetes Care Inc, US Appl. 2012/0,138,484

An analyte sensor consists of a counter electrode and a working electrode with a sensing layer disposed on it. This layer comprises an analyte-responsive enzyme, a redox mediator containing an Os-containing complex or a Ru-containing complex having at least one pyridine boronic acid ligand and a thickener comprising urea, a urea derivative, urethane, a urethane derivative, a polyvinyl pyrrolidone polymer or a polyvinyl pyrrolidone polymer derivative. It is claimed that the analyte sensor has ≥90% of its initial sensitivity after ≥14 days.


Integrated Circuit Device

R. N. Akolkar and J. S. Clarke, US Appl. 2012/0,161,320

An integrated circuit device consists of a substrate with a layer of dielectric material on its surface. The dielectric material has a depression where one side is in contact with a metal layer selected from Ru, Pt, Ir, Pd, Re and Rh, preferably Ru, plus Co. A Cu seed layer is electrodeposited into the depression with a Co dopant. The metal layer is 1–4 nm thick.

Ruthenium Sputtering Target

General Research Institute for Nonferrous Metals, Chinese Appl. 102,485,378; 2012

A Ru sputtering target is heated at a rate of 50°C min−1 from room temperature to 1200°C, it is then heated at a rate of 25°C min−1 to 1400–1700°C and hot pressed at 35 MPa for 10–60 min. The resulting Ru sputtering target has a relative density >98%, the average grain size is


Novel Platinum Nanoparticles

Tata Chemicals Ltd, World Appl. 2012/095,863

A modified Pt NP has a mercapto alkyl acid and optionally an alkyl thiol attached to it and is supported on a substrate selected from rice husk ash, mesoporous silica, microporous silica, nanosilica and alumina. This is prepared by reacting a solution comprising of a Pt precursor and a mercapto alkyl acid with a reducing agent. This second solution is heated to 50–100°C. The molar ratio of the mercapto alkyl acid and the alkyl thiol varies in the range of 0.25–100. The size of Pt NP varies in the range of 1–1000 nm and the Pt content is 5–98 wt%.


Manufacturing Osmium Membrane

Beijing Institute of Satellite Environmental Engineering, Chinese Appl. 102,453,932; 2012

The process for manufacturing Os membrane comprises: (a) cleaning the quartz glass substrate, drying, preheating for 5–10 min under vacuum; (b) depositing a Cr layer and a Au layer both having a thickness of 5–20 nm by a PVD method; (c) cleaning to remove the residual reagent; (d) vacuum drying to obtain the Cr/Au coated quartz glass; (e) electroplating the Cr/Au coated quartz glass as cathode and Pt gauze electrode anode for 10 min whilst controlling the current density of 2.5–3.5 A dm−3, changing a new electroplating solution and re-electroplating for >10 min whilst controlling the current density of 2.5–3.5 A dm−3 to form an Os layer of thickness >1 μm. The Os electroplating solution is made after removing pinholes and reducing electrode surface tension by adding a surfactant to distilled water. This is then boiled, cooled and diluted to obtain 0.01 g l−1 surfactant solution. The complexing agents NH2SO3H (25 g l−1) and NH2SO3NH4 (10 g l−1) are added to completely dissolve (NH4)2OsCl6 (10 g l−1). This method can avoid the cracking phenomenon during Os electroplating and increase the thickness of the Os layer. The membranes can be used for preparing space atomic oxygen environmment detectors.

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