ABSTRACTS: July 2007
ABSTRACTS: July 2007
of current literature on the platinum metals and their alloys
Cyclic Oxidation of Ru-Containing Single Crystal Superalloys at 1100°C
Q. FENG, B. TRYON, L. J. CARROLL and T. M. POLLOCK, Mater. Sci. Eng.: A, 2007, 458, (1–2), 184–194
The cyclic oxidation behaviour at 1100°C of Ru (3.5–9 at.%)-containing Ni-base single crystal superalloys (1) with Cr additions (0–8 at.%) has been investigated. High levels of Cr additions (8 at.%) significantly improved oxidation resistance. A multilayered scale formed on (1); this generally consisted of an external layer of NiO, an intermediate layer of spinel and an α-Al2O3 inner layer (2). (2) improved oxidation performance. Ru-rich precipitates were observed in the spinel layer of (1) which displayed poor oxidation resistance.
Electronic Properties of the Semiconductor RuIn3
D. BOGDANOV, K. WINZER, I. A. NEKRASOV and T. PRUSCHKE, J. Phys.: Condens. Matter, 2007, 19, (23), 232202
Single crystals of RuIn3 (1) were grown using the flux method with In as reactant and flux medium. Temperature-dependent measurements of the resistivity of (1) show a semiconducting behaviour, in contrast to previously published results. In the high-temperature range the semiconducting gap is 0.4–0.5 eV. An anisotropy of the resistivity along  and  orientations of the tetragonal (1) was observed.
Organometallic Molecular Materials: Self-Assembly through Hydrogen Bonding of an Organoplatinum Network Structure with Zeolite-Like Topology
F. ZHANG, M. C. JENNINGS and R. J. PUDDEPHATT, Chem. Commun., 2007, (15), 1496–1498
[Pt(OH)2Me2(dpa)] (1) (dpa = di-2-pyridylamine) was formed by oxidation of [PtMe2(dpa)] by H2. [Pt2(μ-OH)2Me4(dpa)2][B(OH)(C6F5)3]2 (2) was obtained by abstraction of a hydroxo ligand from (1) by reaction with B(C6F5)3. (1) and (2) contain both H-bonding PtOH groups and NH groups. Self-assembly of (1) to form a complex network structure gave the first “organometallic zeolite”.
Solvent-Free Synthesis of Metal Complexes
A. LAZUEN GARAY, A. PICHON and S. L. JAMES, Chem. Soc. Rev., 2007, 36, (6), 846–855
Polymeric PtCl2 will react with solid phosphines after grinding in a ball mill to give cis-[PtCl2(PPh3)2], which can subsequently react with solid K2CO3 to give [Pt(CO3)(PPh3)2]. Also, supramolecular host structures, such as a tetraplatinum square and a nano-scale bowl-shaped hexapalladium cage, self-assemble with remarkable efficiency in the solid state. (39 Refs.)
Electrochemical Performance of Nano-Pt-Supported Carbon Anode for Lithium Ion Batteries
W.-S. KIM, H. S. KIM, I.-S. PARK, Y. KIM, K.-I. CHUNG, J. K. LEE and Y.-E. SUNG, Electrochim. Acta, 2007, 52, (13), 4566–4571
The title anode (1) was prepared by supporting Pt nanoparticles onto C powder. The Pt nanoparticles on the C surface helped to suppress the solvent decomposition reaction: a protective film was formed as soon as (1) had contact with the electrolyte. In addition, the Pt nanoparticles act as catalyst reaction sites to improve the Li discharge reaction.
Compositional and Electrochemical Characterization of Noble Metal–Diamondlike Carbon Nanocomposite Thin Films
N. MENEGAZZO, C. JIN, R. J. NARAYAN and B. MIZAIKOFF, Langmuir, 2007, 23, (12), 6812–6818
Pt– and Au–diamondlike C (DLC) nanocomposite films (1) were deposited onto Si substrates by modified pulsed laser deposition. Cross-sectional TEM revealed that metal was present as arrays of noble metal islands embedded within the DLC matrix. (1) exhibited greater conductivity than their metal-free counterparts. The electrochemical properties of (1) were studied using quasi-reversible redox couples.
Photocatalytic Oxidation of NOx by Pt-Modified TiO2 Under Visible Light Irradiation
Y. ISHIBAI, J. SATO, S. AKITA, T. NISHIKAWA and S. MIYAGISHI, J. Photochem. Photobiol. A: Chem., 2007, 188, (1), 106–111
Photooxidation of NOx was carried out using TiO2 (Ishihara ST-01) treated with H2PtCl6. Pt-modified TiO2 was obtained with different ligand structures according to the Pt treatment method. TiO2 photocatalysts with certain Pt complexes produced significant photocatalytic activity under visible light irradiation without decreasing photoactivity under UV light irradiation. The visible-light-induced photocatalytic activity depended on the amount of Pt.
An Investigation on Palladium Sulphide (PdS) Thin Films as a Photovoltaic Material
I. J. FERRER, P. DÍAZ-CHAO, A. PASCUAL and C. SÁNCHEZ, Thin Solid Films, 2007, 515, (15), 5783–5786
Polycrystalline PdS thin films (1) with tetragonal structure were grown by direct sulfuration of Pd layers. (1) exhibited a Seebeck coefficient, S = −250 ± 30 µV K−1. Electrical resistivity of (1), measured by a four contact probe, was (6.0 ± 0.6) × 10−2 Ω cm. Hall effect measurements confirmed n-type conductivity. Optical absorption coefficient in the range of photon energies hυ > 2.0 eV was higher than 105 cm−1.
Iridium(III) Complexes Bearing Quinoxaline Ligands with Efficient Red Luminescence Properties
K. TANI, H. FUJII, L. MAO, H. SAKURAI and T. HIRAO, Bull. Chem. Soc. Jpn., 2007, 80, (4), 783–788
Excellent quantum efficiencies (50–79%) for photoluminescence were attained for cyclometallated Ir(III) complexes (1) bearing 2,3-diphenylquinoxalines in CH2Cl2. Luminescence peak wavelengths of (1) were within the preferred range of 653–671 nm in thin films. The most vivid red electrophosphorescence was achieved with an acetylacetonato Ir complex bearing 2,3-diphenylquinoxaline.
ELECTRODEPOSITION AND SURFACE COATINGS
In Situ Raman Spectroscopy of Annealed Diamondlike Carbon–Metal Composite Films
C. JIN, H. ZHOU, S. GRAHAM and R. J. NARAYAN, Appl. Surf. Sci., 2007, 253, (15), 6487–6492
Films of diamondlike C, diamondlike C–Pt composite and diamondlike C–Au composite were annealed to 523°C. The Raman spectra for these films were fitted using a two-Gaussian function. The variations of the G-peak position, the D-peak position, and the ID/IG ratio were examined as a function of temperature. The diamondlike C film exhibited greater thermal stability than the diamondlike C–noble metal composite films.
Synthesis of PVP Stabilized Cu/Pd Nanoparticles with Citrate Complexing Agent and Its Application as an Activator for Electroless Copper Deposition
S. H. Y. LO, Y.-Y. WANGM and C.-C. WAN, J. Colloid Interface Sci., 2007, 310, (1), 190–195
Cu/Pd nanoparticles (1) were synthesised in aqueous solution using trisodium citrate as additive. The protecting agent PVP was added after the citrate. (1) exist in a stable suspension. XPS of (1) revealed small amounts of oxidised Pd on the surface and the existence of zerovalent Cu and oxidised Cu. (1) exhibited catalytic activity comparable to that of conventional Pd/Sn activator. (1) have potential as an activator for electroless Cu deposition in the PCB industry.
Electrodeposition of Magnetic CoPd Thin Films: Influence of Plating Condition
F. M. TAKATA and P. T. A. SUMODJO, Electrochim. Acta, 2007, 52, (20), 6089–6096
The title thin films (1) were electrodeposited from a chloride plating bath containing glycine as additive. The Co content in (1) could be varied from 6.4–94.0 at.% by controlling the pH and [Co2+]/[Pd2+] ratio in the bath. Current densities > 50 mA cm−2 gave deposits with a typical ‘cauliflower’ morphology. For current densities < 25 mA cm−2 cracks were observed. XRD showed that (1) were amorphous. The magnetic properties for (1) revealed that the coercivity (Hc) values ranged from 84–555 Oe and the magnetic saturation (Ms) from 0–1.73 T.
APPARATUS AND TECHNIQUE
Pd Encapsulated and Nanopore Hollow Fiber Membranes: Synthesis and Permeation Studies
B. K. R. NAIR and M. P. HAROLD, J. Membrane Sci., 2007, 290, (1–2), 182–195
“Pd encapsulated” (1) and “Pd nanopore” (2) membranes on α-Al2O3 hollow fibres were synthesised by sol slip casting, film coating, and electroless plating steps. The unaged (1) exhibited good performance with ideal H2/N2 separation factors of 3000–8000 and H2 flux ∼ 0.4 mol m−2 s−1 at 370°C. The unaged (2) had a lower initial flux and permselectivity, but exhibited superior performance after 200 h.
HCN Synthesis from Methane and Ammonia over Platinum
S. DELAGRANGE and Y. SCHUURMAN, Catal. Today, 2007, 121, (3–4), 204–209
TAP (temporal analysis of products) experiments were conducted for the synthesis of HCN from NH3 and CH4 over Pt black. At 1173 K the HCN production rate depends on the order of introducing the reactants. HCN is formed rapidly on the CH4 pulse just after introducing NH3. A slow formation of HCN is observed on the NH3 pulse that follows a CH4 pulse. The rate-determining step for the formation of HCN is the NH3 decomposition rate.
Synthesis and Characterization of Pt/Mg(Al)O Catalysts Obtained From Layered Double Hydroxides by Different Routes
O. LORRET, S. MORANDI, F. PRINETTO, G. GHIOTTI, D. TICHIT, R. DURAND and B. COQ, Microporous Mesoporous Mater., 2007, 103, (1–3), 48–56
Pt-containing Mg/Al layered double hydroxides at different Pt loadings (0–3.2 wt.%) were prepared by coprecipitation, impregnation and sol-gel methods. After activation and reduction treatments, Pt nanoclusters interacting with Mg(Al)O supports were obtained. The behaviour of Pt/Mg(Al)O systems as multifunctional catalysts was investigated in the cascade reaction between benzaldehyde and propanal.
Pd-Based Sulfated Zirconia Prepared by a Single Step Sol–Gel Procedure for Lean NOx Reduction
E. M. HOLMGREEN, M. M. YUNG and U. S. OZKAN, J. Mol. Catal. A: Chem., 2007, 270, (1–2), 101–111
The title catalysts (1) were obtained via a single-step sol-gel procedure. Tetragonal zirconia was formed at lower temperatures; larger zirconia crystallites were obtained when Pd was added to the gel. Raman spectra of (1) calcined at 700°C showed both the tetragonal and the monoclinic phases, indicating a surface phase transition. (1) were active for the reduction of NO2 with CH4 under lean conditions. (1) calcined at 700°C were much more active than (1) calcined at 600°C, despite the observed transition to the monoclinic phase.
XPS and 1H NMR Study of Thermally Stabilized Rh/CeO2 Catalysts Submitted to Reduction/Oxidation Treatments
C. FORCE, E. ROMÁN, J. M. GUIL and J. SANZ, Langmuir, 2007, 23, (8), 4569–4574
Rh/CeO2 (1) was prepared by incipient wetness impregnation of CeO2 with a solution of Rh(NO3)3. (1) was submitted to different H2 reduction, Ar+ sputtering, and oxidation treatments. Below 473 K, reduction increased the amount of OH and Ce3+ species; above this temperature, reduction produced O vacancies at the surface of the support. From 1H NMR, the metal dispersion was deduced and the mean size of the metal particles (38 Å) estimated.
Screening of a Modular Sugar-Based Phosphite-Oxazoline Ligand Library in Asymmetric Pd-Catalyzed Heck Reactions
Y. MATA, O. PÀMIES and M. DIÉGUEZ, Chem. Eur. J., 2007, 13, (12), 3296–3304
A library of phosphite-oxazoline ligands (1) derived from D-glucosamine was synthesised. (1) were successfully screened in the Pd-catalysed Heck reaction of several substrates with high regio- (≤ 99%) and enantioselectivities (ee's ≤ 99%) as well as with improved activities. The catalytic activity was highly affected by the oxazoline and biarylphosphite substituents and the axial chirality of the biaryl moiety of (1).
Development of a Concise Scaleable Synthesis of 2-Chloro-5-(pyridin-2-yl) Pyrimidine via a Negishi Cross-Coupling
C. PÉREZ-BALADO, A. WILLEMSENS, D. ORMEROD, W. AELTERMAN and N. MERTENS, Org. Process Res. Dev., 2007, 11, (2), 237–240
A Negishi cross-coupling between an in situ prepared 2-pyridylzinc chloride and 5-iodo-2-chloropyrimidine catalysed by Pd(PPh3)4 afforded 2-chloro-5-(pyridin-2-yl) pyrimidine (1) in one step. Chromatography can be omitted as a convenient purification was developed. The method has been used on a mini-plant scale to produce 16 kg of (1). The Pd and Zn content of (1) was acceptable for the production of its derived API, a selective PDE-V inhibitor.
Nanoscale Current Imaging of the Conducting Channels in Proton Exchange Membrane Fuel Cells
D. A. BUSSIAN, J. R. O'DEA, H. METIU and S. K. BURATTO, Nano Lett., 2007, 7, (2), 227–232
A Pt-coated AFM tip was used as a nanoscale cathode in a PEMFC. Inhomogeneous distributions of conductive surface domains at several length scales were found. Phase current correlation microscopy showed that a large number (∼ 60%) of the aqueous domains present at the surface of the operating Nafion membrane were inactive.
Surface-Modified Carbons as Platinum Catalyst Support for PEM Fuel Cells
A. GUHA, W. LU, T. A. ZAWODZINSKI and D. A. SCHIRALDI, Carbon, 2007, 45, (7), 1506–1517
The ability of functionalised high surface area graphitic (C nanofibres) and amorphous (activated C) C to homogeneously support Pt particles was investigated. Functionalisation by conc. acid treatment created various O carrying functionalities on the C surfaces. Chemical reduction of the Pt precursor complex, using milder reducing agents at 75–85°C, and using ethylene glycol at 140°C, gave the smallest Pt particle sizes. XPS confirmed the existence of Pt in (primarily) its metallic state on the functionalised C.
Characterization and PEMFC Testing of Pt1−xMx (M = Ru, Mo, Co, Ta, Au, Sn) Anode Electrocatalyst Composition Spreads
D. A. STEVENS, J. M. ROULEAU, R. E. MAR, A. BONAKDARPOUR, R. T. ATANASOSKI, A. K. SCHMOECKEL, M. K. DEBE and J. R. DAHN, J. Electrochem. Soc., 2007, 154, (6), B566–B576
Pt1−xMx random alloy samples were deposited via magnetron sputtering through shadow masks onto a nanostructured thin-film support for testing in a 64-electrode PEMFC. CO stripping voltammograms and H2 oxidation polarisation curves with pure H2 and reformate (≤ 50 ppm CO) were measured. Ru, Mo, and Sn were confirmed to improve the CO tolerance of Pt, although the intrinsic H2 oxidation activity of Pt decreased significantly as the Sn content increased.
Autothermal Reforming of Gasoline on Rh-Based Monolithic Catalysts
A. QI, S. WANG, C. NI and D. WU, Int. J. Hydrogen Energy, 2007, 32, (8), 981–991
0.3 wt.% Rh/3 wt.% MgO/20 wt.% CeO2-ZrO2 supported on cordierite monolith was used for ATR. At 650–800°C, O2/C molar ratio of 0.38–0.45 and H2O/C ratio of 2.0, octane was fully converted into reformate (+ small amount of CH4), whereas toluene converted into CH4-free reformate at a relatively higher temperature. A 1 kW gasoline fuel processor for fuel cell application was successfully operated at a (H2 + CO) throughput of 0.9–1.0 m3 h−1 for 60 h.
Corrosion Behaviour of FePt-Based Bulk Magnets in Artificial Saliva Solution
A. GEBERT, S. ROTH, R. GOPALAN, A. A. KÜNDIG and L. SCHULTZ, J. Alloys Compd., 2007, 436, (1–2), 309–312
The corrosion behaviour of Fe50Pt50, Fe35Pt35P30 and Fe53Pt44C3 magnets was investigated in artificial saliva solution at 37°C. Electrochemical polarisation measurements and SEM showed that the alloys exhibit a Pt-like behaviour (highly stable). Enhanced corrosion activity did not occur when these alloys were coupled with commercial Fe- and CoCr-based dental alloys. A low-corroding state was attained in combination with the dental spring steel Fe-18Cr-18Mn-2Mo-1N.