A. C. ALBÉNIZ, P. ESPINET, O. LÓPEZ-CIMAS and B. MARTÍN-RUIZ, Chem. Eur. J., 2005, 11, (1), 242–252
LINK http://dx.doi.org/10.1002/chem.200400612
[Pd2(μ-R)2(η3-allyl)2] (R = haloaryl, mesityl) were prepared. The haloaryl complexes exchange between their cis and trans isomers (relative to the orientation of the two allyl groups in the dimer) by solvent-assisted associative bridge splitting. Stable aryl bridges are favoured by ancillary ligands of small size and lacking electron lone pairs, and aryl ligands reluctant to be involved in homo and hetero C–C coupling.
S. BASU, S.-M. PENG, G.-H. LEE and S. BHATTACHARYA, Polyhedron, 2005, 24, (1), 157–163
LINK http://dx.doi.org/10.1016/j.poly.2004.10.015
The pic ligands of [M(pic)3] (1) (M = Rh, Ir; Hpic = picolinic acid) are coordinated as bidentate N,O-donors. A water of crystallisation molecule is H bonded to the carboxylate fragments of two adjacent (1) and acts a bridge between the individual (1). (1) are diamagnetic and show intense MLCT transitions in the visible region. CV on (1) shows a M(III)–M(IV) oxidation and a ligand-centred reductive response.
Y. OBORA, Y. K. LIU, L. H. JIANG, K. TAKENAKA, M. TOKUNAGA and Y. TSUJI, Organometallics, 2005, 24, (1), 4–6
LINK http://dx.doi.org/10.1021/om049227j
The title complexes (1) exhibited dynamic behaviour with size-selective molecular encapsulation. Variable-temperature 31P{1H} NMR measurements were carried out in the presence of various molecules (1). (1) were divided into three groups, depending on the maximum projection area of the solvent-accessible surface, A: < 45 Å2, 45–68 Å2, and > 68 Å2. Molecules with A of 45–68 Å2 just fit in the cavity and slow the dynamic behaviour.
Y. MATSUO, A. IWASHITA and E. NAKAMURA, Organometallics, 2005, 24, (1), 89–95
LINK http://dx.doi.org/10.1021/om049333l
Ir(η5-C60Me5)(CO)2 (1) was obtained from the reaction of K(C60Me5) with [IrCl(CO)2]2 in MeCN/THF. Oxidation of the Ir atom of (1) by I2 gave an Ir(III) complex, Ir(η5-C60Me5)I2(CO) (2). The iodo and carbonyl ligands of (2) can be readily replaced by alkyl, alkynyl, phosphine, and isonitrile ligands. (2) may be used as catalysts for organic synthesis.
L. KONDRACHOVA, K. E. PARIS, P. C. SANCHEZ, A. M. VEGA, R. PYATI and C. D. RITHNER, J. Electroanal. Chem., 2005, 576, (2), 287–294
LINK http://dx.doi.org/10.1016/j.jelechem.2004.11.003
Pt phenylethynyl complexes exhibited irreversible oxidations in benzene/MeCN near +1.2 V vs. Ag|AgCl. However, trans-bis(tri-n-butylphosphine) bis(phenylethynyl)platinum(II) underwent reduction in THF at –2.786 V. Photophysical measurements established that as the phenylethynyl chain length increases, the absorbance wavelength increases. The emission wavelength shows a weak but similar trend.
M. A. BANGAR, K. RAMANATHAN, M. YUN, C. LEE, C. HANGARTER and N. V. MYUNG, Chem. Mater., 2004, 16, (24), 4955–4959
LINK http://dx.doi.org/10.1021/cm048931n
Dimensionally controlled growth of a single Pd nanowire (1) between premicrofabricated Au electrodes was achieved using an electrochemical method. (1) of 100 nm, 500 nm, and 1 μm wide and 2.5 μm long channels (length-to-diameter ratio ~ 2.5–25) were grown. Current of –100 nA was used.
Y.-Z. HU, M. H. WILSON, R. ZONG, C. BONNEFOUS, D. R. McMILLIN and R. P. THUMMEL, Dalton Trans., 2005, (2), 354–358
LINK http://dx.doi.org/10.1039/b415021j
[Pt(1)Cl]+ (2) ((1) = 2-(8'-quinolinyl)-1,10-phenanthroline) was prepared. The six-membered chelate ring in (2) gives relief to the angle strain as well as some non-planarity in bound (1). In CH2Cl2 (2) exhibited higher energy charge-transfer absorption, but slightly lower energy emission than [Pt(3)Cl]+ ((3) = 2-(2'-pyridyl)-1,10-phenanthroline).
N. YOSHIKAWA, T. MATSUMURA-INOUE, N. KANEHISA, Y. KAI, H. TAKASHIMA and K. TSUKAHARA, Anal. Sci., 2004, 20, (12), 1639–1644
LINK http://dx.doi.org/10.2116/analsci.20.1639
The title complexes include [RuII2Cl2(dpp)(terpy)2]2+ (1) and [IrIIIRuIICl2(dpp)(terpy)2]3+ (2) (dpp = 2,3-bis(2-pyridyl)pyrazine). The absorption spectra of (1) and (2) exhibit ligand-centred bands in the UV region and MLCT bands in the visible region. The HOMO is based on Ru, and the LUMO is dpp-based.
F. AIGA and T. TADA, Sol. Energy Mater. Sol. Cells, 2005, 85, (3), 437–446
LINK http://dx.doi.org/10.1016/j.solmat.2004.04.020
The title Ru complex (1) was designed based on the DFT MO calculations with PBE0 functional. (1) is a modification of the Ru black dye (2), with the NCS ligands of (2) being replaced by C5H4NS ligands. (1) has a higher electron transfer rate from redox systems to oxidised dyes and higher absorption efficiency to the solar spectrum.
A. F. NOGUEIRA, S. H. TOMA, M. VIDOTTI, A. L. B. FORMIGA, S. I. CÓRDOBA DE TORRESI and H. E. TOMA, New J. Chem., 2005, 29, (2), 320–324
LINK http://dx.doi.org/10.1039/b411122b
Na6[{RuII(dicarboxybipyridine)2Cl}2(BPEB)] (1) (BPEB = trans-1,4-bis[2-(4-pyridyl)ethenyl]benzene) exhibits an electrochromic effect when reduced. The carboxylate groups of the bipyridine allow strong attachment to the surface of TiO2. This contributes to an efficient and reversible electron transfer from the oxide to the chromophoric ligand, colouring the oxide film blue. (1) also has a high photon-to-electron conversion efficiency when applied as a photoanode in a dye sensitised solar cell.
W.-H. LIN and H.-F. CHANG, Surf. Coat. Technol., 2005, 194, (1), 157–166
LINK http://dx.doi.org/10.1016/j.surfcoat.2004.07.089
Sequential electroless plating on porous stainless steel was used to prepare Pd-Ag membranes. AFM established that lower skin layer roughness and lower deposition rate were related. EDS confirmed the Pd-Ag deposit over and inside of the porous substrate to be homogeneous.
D. A. PACHECO TANAKA, M. A. LLOSA TANCO, S. NIWA, Y. WAKUI, F. MIZUKAMI, T. NAMBA and T. M. SUZUKI, J. Membrane Sci., 2005, 247, (1–2), 21–27
LINK http://dx.doi.org/10.1016/j.memsci.2004.06.002
For the title process, seeding of Pd nanoparticles (1) on an α-Al2O3 tube allowed codeposition of Pd and Ag. (1) were distributed by dip-coating with Pd acetate or [Pd(acac)2] in organic solvents followed by reduction with alkaline hydrazine solution. After simultaneous deposition, alloying of Pd and Ag was carried out at 500ºC for 4 h in H2.
R.-S. CHEN, H.-M. CHANG, Y.-S. HUANG, D.-S. TSAI and K.-C. CHIU, Nanotechnology, 2005, 16, (1), 93–97
LINK http://dx.doi.org/10.1088/0957-4484/16/1/019
The morphological evolution of IrO2 1D nanocrystals (1) via MOCVD has been observed. (1) result from a decrease in the degree of interface instability. (1) occur from triangular/wedged nanorods via incomplete/scrolled nanotubes to square nanotubes and square nanorods. The polycrystalline films composed of continuous 3D grains belong to the most stable form as compared to the 1D nanocrystals.
I. VJUNITSKY, P. P. BANDYOPADHYAY, St. SIEGMANN, M. DVORAK, E. SCHÖNFELD, T. KAISER, W. STEURER and V. SHKLOVER, Surf. Coat. Technol., 2005, 192, (2–3), 131–138
LINK http://dx.doi.org/10.1016/j.surfcoat.2004.09.028
The normal value range for the thermal conductivity of the title alloys is 10–20 W m–1 K–1 at room temperature, but can be reduced to ~ 3.5 W m–1 K–1 by modifying the alloy composition. A fused and subsequently pulverised Al-Ni-Ru alloy was deposited on a Ni-based superalloy (modified CMSX-4) using vacuum and atmospheric plasma spraying. The coatings had favourable coating–substrate adhesion. A segregated intermetallic phase was detected at the Al50Ni40Ru10/modified CMSX-4 interface.
B. K. GAN, B. A. LATELLA and R. W. CHEARY, Appl. Surf. Sci., 2005, 239, (2), 237–245
LINK http://dx.doi.org/10.1016/j.apsusc.2004.05.269
Ultra-thin Pt/C and W/C multilayer films (1) were fabricated using DC magnetron sputtering. The bilayer period and the total number of layers were varied to ascertain the X-ray reflectance response. XPS established that a distinct intermixing layer develops in (1). (1) are mechanically reliable and have excellent adhesion. Hardness and Young's modulus improved with increasing number of layers. (1) have potential as mirrors for high energy X-ray applications.
Y. ZHANG, M. KOMAKI and C. NISHIMURA, J. Membrane Sci., 2005, 246, (2), 173–180
LINK http://dx.doi.org/10.1016/j.memsci.2004.09.002
H2 permeation of Pd and Pd-25Ag membranes supported by V-15Ni was investigated at 423–673 K. The Pd-25Ag membrane was more resistant to H-induced cracking and grain growth. H permeation of the Pd-25Ag/V-15Ni membrane (1) was carried out at 573 and 673 K for 200 h. At 573 K, small amounts of oxide formed on the Pd-Ag surface. Whisker and fissure-oxide morphologies were dominant on the exit and entrance side of (1), respectively, along with severe metallic interdiffusion, at 673 K.
I. SOBCZAK, M. ZIOLEK and M. NOWACKA, Microporous Mesoporous Mater., 2005, 78, (2–3), 103–116
LINK http://dx.doi.org/10.1016/j.micromeso.2004.10.001
The title catalysts were prepared via impregnation of NbMCM-41 with Pt(NH3)4(NO3)2 or H2PtCl6 (1 wt.% of Pt). Smaller size Pt clusters were obtained with H2PtCl6. A FTIR study with NO + O2 + C3H6 indicated that Pt/NbMCM-41 has potential for the SCR process. The NbO– species enhance the oxidative activity in NO → NO2, whereas the Pt species is responsible for hydrocarbon activation. NbMCM-41 acts as storage for the nitrate/nitrite species.
R. STROBEL, S. E. PRATSINIS and A. BAIKER, J. Mater. Chem., 2005, 15, (5), 605–610
LINK http://dx.doi.org/10.1039/b413198c
Flame spray pyrolysis was used to prepare Pd nanoparticles (< 5 nm) supported on La-stabilised Al2O3 (1) with specific surface areas of 50–180 m2 g–1. (1) was tested for the catalytic combustion of CH4. (1) exhibited excellent thermal stability in terms of specific surface area up to 1200ºC and retarded γ- to α-Al2O3 transformation. (1) was tested as-prepared and after sintering at 1000ºC (Pd particles, 50–150 nm). All the materials exhibited similar catalytic performance after an initial conditioning cycle if the temperature was cycled several times (200–1000ºC).
G. PECCHI, P. REYES, R. ZAMORA, T. LÓPEZ and R. GÓMEZ, J. Chem. Technol. Biotechnol., 2005, 80, (3), 268–272
LINK: http://dx.doi.org/10.1002/jctb.1120
Pd-CeO2-supported catalysts, prepared by the sol-gel technique, were used for the catalytic combustion of CH4. The addition of CeO2 to Al2O3 gave a highly dispersed catalyst when compared with their ZrO2 counterparts. However, the catalytic activity of the Pd-CeO2-ZrO2 series is higher, due to the Pd having a larger particle size.
N. C. KING, C. DICKINSON, W. ZHOU and D. W. BRUCE, Dalton Trans., 2005, (6), 1027–1032
LINK http://dx.doi.org/10.1039/b415288c
Mesoporous silicates were prepared by templating on the hexagonal mesophase of bis(2,2'-bipyridine)(4,4'-dinonadecyl-2,2'-bipyridine)ruthenium(II) dichloride using liquid-crystal templating. On calcination, the surfactant template was removed, except for the central Ru ion that was oxidised to RuO2 nanoparticles (1) within the pores. (1) were active in catalysing the oxidation of H2O by acidic CeIV.
J. HU and Y. LIU, Langmuir, 2005, 21, (6), 2121–2123
LINK http://dx.doi.org/10.1021/la0471902
The Pd nanoparticles (1) recovered from the N,N-dihexylcarbodiimide–Pd nanoparticle composite catalysts used in Suzuki cross-couplings, were found to transform from spherical-shape to larger needle-shaped crystals. (1) aggregated into nanosized blackberry-like assemblies (100–200 nm) as a result of Ostwald ripening. In a second type of ripening, atomic rearrangement occurred and (1) transformed into needle-shaped nanocrystals. These observations will be important for the future design and optimisation of durable nanoparticle catalysts.
B. P. BUFFIN, J. P. CLARKSON, N. L. BELITZ and A. KUNDU, J. Mol. Catal. A: Chem., 2005, 225, (1), 111–116
LINK http://dx.doi.org/10.1016/j.molcata.2004.08.035
Pd(OAc)2 stabilised by 2,2'-biquinoline-4,4'-dicarboxylic acid was used in the aerobic oxidation of primary and secondary alcohols. H2O was used as the reaction solvent, with air as the oxidant. Aliphatic primary alcohols were fully oxidised to carboxylic acid products. Secondary alcohols gave the corresponding ketones. The catalyst can be recycled.
K. R. J. THOMAS, J. T. LIN, Y.-T. TAO and C.-H. CHUEN, Chem. Mater., 2004, 16, (25), 5437–5444
LINK http://dx.doi.org/10.1021/cm048794u
Oxadiazole-incorporated carbazoylylamines (1) were synthesised using Pd catalysed C–N coupling reactions with Pd(dba)2/P(t-Bu)3 catalyst and t-BuONa base. The reactions were best carried out in toluene at 80ºC. Yields of (1) ranged from 75–95%. (1) were purified by reprecipitating twice from CH2Cl2/MeOH before application in the electroluminescent devices, such as OLEDs.
H. ZHENG, M. LI, H. CHEN, R. LI and X. LI, Chin. J. Catal., 2005, 26, (1), 4–6
The hydroformylation of 1-hexene catalysed by HRh(CO)(TPPTS)3 complexes (1) (TPPTS = triphenylphosphine-m-trisulfonic acid trisodium salt) was carried out in 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim]BF4). The activity and selectivity of (1) in [bmim]BF4 were higher than those in other ionic liquids. The TOF of 1-hexene and selectivity for aldehyde were 1508 h–1 and 92%, respectively, under optimum conditions. The high activity of (1) is due to its higher solubility in [bmim]BF4 and to the absence of halide ions.
E. BUSTELO and P. H. DIXNEUF, Adv. Synth. Catal., 2005, 347, (2–3), 393–397
LINK http://dx.doi.org/10.1002/adsc.200404219
While [(p-cymene)RuCl(PR3)][OTf] (PR3) (PR3 = PCy3, PPh3) catalyse the propargylation of furan or 2-methylfuran by the alkynol HCºCCH(OH)Ph in moderate yield, [(p-cymene)RuCl(CO)(PR3)][OTf] are more active. The stoichiometric reaction of [(p-cymene)RuCl(PR3)][B(ArF)4] (ArF = 3,5-(CF3)2C6H3) and the alkynol resulted in the in situ formation, via allenylidene and hydroxycarbene intermediates, of [(p-cymene)RuCl(CO)(PR3)]B(ArF)4].
I. C. LENNON and J. A. RAMSDEN, Org. Process Res. Dev., 2005, 9, (1), 110–112
LINK http://dx.doi.org/10.1021/op049838n
Catalytic asymmetric transfer hydrogenation of 1-aryl-2-imidazol-1-yl-ethanones with formic acid using [(R,R)-TsDPEN]Ru(Cymene)Cl gave homochiral 1-aryl-2-imidazol-1-yl-ethanols. The hydrogenation was carried out under mild conditions at a molar substrate-to-catalyst ratio of 1000–2000. Bisphosphino Ru diamine complexes were found to be ineffective.
Z. LIU, J. S. WAINRIGHT and R. F. SAVINELL, Chem. Eng. Sci., 2004, 59, (22–23), 4833–4838
LINK http://dx.doi.org/10.1016/j.ces.2004.09.024
A micro-band electrode cell was used to investigate the ORR for a Pt/polybenzimidazole–phosphoric acid system. The obtained Tafel plots were linear over four orders of magnitudes of kinetic current density. Both the kinetic parameters and the mass transport data were comparable to those of a Pt/phosphoric acid system.
J. ZENG and J. Y. LEE, J. Power Sources, 2005, 140, (2), 268–273
LINK http://dx.doi.org/10.1016/j.jpowsour.2004.08.022
Pt/C and Pt-Co/C were prepared by NaBH4 reduction of metal precursors. Citric acid was used as the complexing agent. The largest Pt-Co particles (12 nm) were formed in alkaline solution and the smallest particles (3.7 nm) in unbuffered solution. XPS showed that Pt is in the metallic state, whereas most of the Co is oxidised. The performance of the Pt-Co/C catalysts in MeOH electrooxidation under acidic conditions showed improvements over the Pt/C catalyst in both activity and CO-tolerance due to the Co addition.
L. XIONG and A. MANTHIRAM, Solid State Ionics, 2005, 176, (3–4), 385–392
LINK http://dx.doi.org/10.1016/j.ssi.2004.08.005
A microemulsion method was used to prepare nanostructured Pt-Ru/C catalysts (1) with different particle sizes. The electrochemical performances of (1) were evaluated in half cells with a mixture of 1 M H2SO4 and 1 M MeOH and in single cell DMFCs. (1) prepared with a water to surfactant molar ratio (W) of 10 exhibited the maximum mass activity with the least charge transfer resistance at an optimum particle size of ~ 5.3 nm. The mass activity decreases and the charge transfer resistance increases as the value of W decreases or increases from 10.
Y. ZHU, Z. KHAN and R. I. MASEL, J. Power Sources, 2005, 139, (1–2), 15–20
LINK http://dx.doi.org/10.1016/j.jpowsour.2004.06.054
Pd-based anode catalysts were used in DFAFCs. Power densities of 255 to 230 mW cm–2 were achieved at relatively high voltages of 0.40 to 0.50 V in formic acid (3.0 to 15.0 M) at 20ºC. A MEA with a Pd catalyst gave some decay in fuel cell performance over several hours. However, the performance can be completely recovered by applying a positive potential at the anode.
J. I. HONG, S. SANKAR, A. E. BERKOWITZ and W. F. EGELHOFF, J. Magn. Magn. Mater., 2005, 285, (3), 359–366
LINK http://dx.doi.org/10.1016/j.jmmm.2004.07.054
Co/Pd multilayers were deposited both at room temperature when thermally activated interfacial intermixing augmented the intentional alloying, and at 77 K. Stressed interfacial alloying is the dominant mechanism. Low temperature measurements indicated the presence of polarised Pd. The hard-axis magnetisation was modelled with a distribution of local perpendicular anisotropies which reflect local composition variations.
K. GURUNATHAN, N. VYAWAHARE and D. P. AMALNERKAR, J. Mater. Sci.: Mater. Electron., 2005, 16, (1), 47–53
LINK http://dx.doi.org/10.1007/s10854-005-4958-5
Ca and Sr ruthenates (1) were prepared by air heating admixtures of the respective carbonates of Ca/Sr and RuO2 at 500, 800 and 900ºC for 15 h. The solid-state reactions occurred at 700–800ºC. These powders still contained carbonate and hence were heated again at 900ºC for 15 h to eliminate the carbonate. The average particle size of (1) is ~ 200–400 nm. The resistor paste was formulated using (1) prepared at 800 or 900ºC and heat treated at 900ºC.