The metal-chain complexes (X)[Os(CO)3(CNBu)]3Mn(CO)5 (X=Cl, Br, I)

In what is a new metal-chain forming reaction, (X)[Os(CO)₃(CNBu^t)]₃Mn(CO)₅ (X=Cl, Br, I) complexes have been prepared by the successive addition of Os(CO)₄(CNBu^t) to Mn(CO)₅(X) in hexane. The crystal structure of the iodo derivative reveals it to contain an approximately linear Os₃ Mn chain of metal atoms.     

UV–Vis observation of different F0 → D0 transitions for both isomeric species in Eu(III) DOTA-like complexes

The presence of the two isomeric species (M and m) of Eu(III) (DOTA-like) complexes has been detected in aqueous solution by UV–Vis absorbance spectrophotometry. It shows that the ⁷F₀ → ⁵D₀ transition in Eu(III) complexes does not only depend on the coordinating atoms present in the first coordination sphere but that it may also be influenced by small differences in the coordination geometry. The absorbance spectra could be well fitted with the K=M/m equilibrium constants measured by NMR. The wavelength variation between the two isomers is found to be 0.20 nm (DTMA), 0.14 nm (DOTA) and about 0.25 nm (DOTAM) (DTMA=1,4,7,10-tetrakis-(methylcarbamoylmethyl)-1,4,7,10-tetraazacyclo-dodecane; DOTA=1,4,7,10-tetraaza-1,4,7,10-tetrakis(carboxymethyl)-cyclododecane; DOTAM=1,4,7,10-tetrakis(carbamoylmethyl)-1,4,7,10-tetraazacyclododecane). This is small enough not to affect the quantitative determination of water coordination equilibria in solution as hydration equilibria produce differences of about 0.5 nm.     

Evaluation of strong acid properties of layered HNbMoO6 and catalytic activity for Friedel–Crafts alkylation

The acid properties and catalytic activity of layered HNbMoO₆ for liquid-phase Friedel–Crafts alkylation are examined. ³¹P MAS NMR spectroscopy using trimethylphosphine oxide as a probe molecule reveals that HNbMoO₆ possesses strong acid sites in the interlayer region. Layered HNbMoO₆ is demonstrated to display remarkable catalytic performance for this reaction, substantially exceeding the activities of niobic acid, niobium–molybdenum mixed oxide, ion-exchange resins, and zeolites. It is determined that benzyl alcohol is intercalated into the HNbMoO₆ interlayer during alkylation to form a monolayer configuration, allowing the strong interlayer acid sites to participate in the reaction.     

Phosphate triester hydrolysis promoted by S3–zinc(II) complexes with a bridged hydroxide: The crystal structure of TtiZn–OP(O)(OC6H4-p-NO2)2, Tti = hydrotris(N-xylyl-2-thioimidazolyl)borate

The bridged μ-hydroxo dinuclear four-co-ordinated zinc(II) complex 2, derived from hydrotris(N-xylyl-2-thioimidazolyl)borate cleaves the P–O bond in tris(p-nitrophenyl)phosphate to form a mixture of a monomeric phosphate diester complex 3 and phenoxo complex 4.     

Interactions between fullerene(C60) and poly(ethylene oxide) in their complexes as revealed by high-resolution solid-state C NMR spectroscopy

A series of poly(ethylene oxide) (PEO)/fullerene(C₆₀) complexes are prepared by lyophilization. The intermolecular interaction and molecular motion in the complex are investigated by solid-state ¹³C NMR spectroscopy. An intense C₆₀ signal due to the intermolecular cross-polarization is observed in the ¹³C CP/MAS spectra of the complex samples, indicating a high degree of dispersion of C₆₀s in the complexes. By measuring the ¹³C spin-lattice relaxation times and ¹H transverse relaxation times of the complex sample and by comparing the static ¹³C spectrum of the pure C₆₀ sample with that of the complex sample, it is demonstrated that there exist n-π interactions between the n-orbitals of the PEO ether oxygen and the π-system of C₆₀. The C₆₀ molecules act as physical cross-links in the amorphous region of PEO, which greatly inhibit the mobility of the surrounding PEO chains, while the rapid isotropic rotation of C₆₀ molecules is also reduced to some extent due to the interactions with the polymer chains.     

Supported dicopper(II) complex catalyst Cu2(II)(μ-Br)2/SiO2: synthesis, characterization and catalytic properties for synthesis of ethylene carbonate

A μ-Br-bridged dicopper(II) complex, namely [Cu₂(μ-Br)₂·6H₂O](ClO₄)₂, has been prepared by metal ion grafting. A supported complex catalyst Cu₂(II)(μ-Br)₂/SiO₂was prepared by modifying the silica surface with NaOEt and anchoring the dicopper(II) complex precursor on the surface of the support. The structure of the complex catalyst has been characterized by elemental analysis, IR spectra and UV–VIS diffusion reflection spectra. Obtained data were compared with published data of the complex. TPD-MS and TPD-IR investigations indicated that CO₂ and ethylene oxide (EO) can be chemisorbed on the surface of the catalyst reversibly in a bridged state and can be desorbed from the surface at 105 and 115 K, respectively. In the high temperature range of 450–573 K, another reversible absorption state for CO₂ was also discovered. For EO, however, a decomposition absorption state was found which gave the dissociated species of CH₄ and CO. TPSR-MS experiments have shown that CO₂ and EO reacted on the surface effectively in the range of 343–413 K. An in situ IR method has been used to study the reactivity of the reactants on the surface of the catalyst, and the target product ethylene carbonate (EC) was detected in the range of 333–413 K. Catalytic experiments indicated that the one-way yield of EC is greater than 8.0% and that the selectivity of EC is greater than 82%. A synergic cyclization reaction pathway is proposed to account for the observed products.     

Influence of OSC Material on the Behaviour of Metallic Pd Catalysts in C2H4 and CO Oxidation as Well as in NO Reduction

The interaction of CO, C₂H₄, O₂, and NO reaction gas compounds over the metallic Pd/Al₂O₃ and Pd/OSC/Al₂O₃ monoliths was investigated in order to understand the behaviour of OSC material in the oxidation and reduction reactions. FT-IR gas analyser was used for the analysis of the product gas composition. Several activity experiments carried out with dissimilar feedstreams have revealed that the Ce _x Zr_1–x O₂ mixed oxide is an oxygen storage compound, which promotes CO and C₂H₄ oxidation as well as NO reduction in particular at low temperatures.     

Ten-vertex osmamonocarbaboranes via arachno and nido {CB9} monocarbaboranes. Polyhedral contraction promoted by [OsCl2(PPh3)3] in MeOH and the crystal and molecular structure of [1-H-1,1-(PPh3)2-2-Ph-3-(OMe)-isocloso-1,2-OsCB8H7]

Reactions of [OsCl₂(PPh₃)₃] 1 with the [NEt₄]⁺ salts of the [6-Ph-nido-6-CB₉H₁₁]⁻ anion 2 and the [arachno-6-CB₉H₁₄]⁻ anion 3 each proceed selectively in methanol solution with the elimination of one boron-containing fragment from the starting cluster polyhedron, yielding together a short series of three novel 10-vertex hydridoosmamonocarbaboranes of isocloso {OsCB₈} cluster geometry.     

SCR of NOx with NH3 over Cu/NaZSM-5 and Cu/HZSM-5 in the presence of decane

The selective catalytic reduction of NO_x with NH₃ in the presence of decane over Cu/ZSM-5 catalysts prepared from H⁺ and Na⁺ZSM-5 precursors were investigated. Cu/NaZSM-5 catalyst showed significantly higher NO_x conversion compared to Cu/HZSM-5. However, the presence of decane decreased the activity of both the catalysts, due to coke formation. Cu/HZSM-5 catalyst showed a larger decline in NO_x conversion with time on stream compared to Cu/NaZSM-5. The higher activity of Cu/NaZSM-5 is attributed, to the promoting effect of Na⁺ cations in the formation of active Cu⁺ and nitrite and nitrate intermediates species and retardation of coke formation.     

Estimation of the effectiveness factor of an outer-sphere redox couple (Fe3+/Fe2+) using rotating disk Ti/IrO2 electrodes of different loading

The effectiveness factor; E _f , defined as the fraction of the surface that participates effectively in a given reaction, is an important parameter when operating three-dimensional (3D) electrodes. The rotating disk electrode (RDE) technique with the Fe³⁺/Fe²⁺ redox couple as a probe reaction has been used for the evaluation of the effectiveness factor of 3D Ti/IrO₂ electrodes with different IrO₂ loading. For this purpose, steady-state polarization measurements using Ti/IrO₂ rotating disk electrodes in 0.5 M Fe³⁺/Fe²⁺ in 1 M HCl were carried out under well-defined hydrodynamic conditions. The low-field approximation relation has been used for the estimation of the exchange current densities j ₀, of the Fe³⁺/Fe²⁺ redox couple. It was found for this redox couple that the effectiveness factor is very low (<2%) and essentially the 2D electrode surface area works effectively in the steady-state polarization measurements.     

Solvothermal synthesis of a novel mixed valence Cu(I)/Cu(II) complex containing sulphate, malate and 4,4-bipyridine, [CuCu2(mal)(SO4)(bpy)2 · H2O]n. Unique binding mode of the malate anion

The reaction of CuSO₄ · 5H₂O with 4,4^′-bipyridine and malic acid at 140 °C under solvothermal conditions afforded a mixed valence three-dimensional coordination polymer [Cu^ICu^II₂(mal)(SO₄)(bpy)₂ · H₂O]_n, (1). The building unit consists of a Cu²⁺-dimer in which copper centers are bridged by malate and sulphate anions. SO₄²⁻ anion further connects dimeric unit with the Cu¹⁺ center. Building units are linked by 4,4^′-bipyridine ligands to form double chains, that are interconnected into 3D network through additional sulphate bridge.     

Kinetic modeling of storage and reduction with different reducing agents (CO, H2, and C2 H4) on a Pt–Ba/-Al2O3 catalyst in the presence of CO2 and H2O

In this paper a global reaction kinetic model is used to understand and describe the NO_x storage/reduction process in the presence of CO₂ and H₂O. Experiments have been performed in a packed bed reactor with a Pt–Ba/γ-Al₂O₃ powder catalyst (1 wt% Pt and 30 wt% Ba) with different lean/rich cycle timings at different temperatures (200, 250, and ) and using different reductants (H₂, CO, and C₂H₄). Model simulations and experimental results are compared. H₂O inhibits the NO oxidation capability of the catalyst and no NO₂ formation is observed. The rate of NO storage increases with temperature. The reduction of stored NO with H₂ is complete for all investigated temperatures. At temperatures above , the water gas shift (WGS) reaction takes place and H₂ acts as reductant instead of CO. At , CO and C₂H₄ are not able to completely regenerate the catalyst. At the higher temperatures, C₂H₄ is capable of reducing all the stored NO, although C₂H₄ poisons the Pt sites by carbon decomposition at . The model adequately describes the NO breakthrough profile during 100 min lean exposure as well as the subsequent release and reduction of the stored NO. Further, the model is capable of simulating transient reactor experiments with 240 s lean and 60 s rich cycle timings.     

Effect of strontium and phosphorus source on the structure,morphology and luminescence of Sr5(PO4)2SiO4:Euphosphor prepared by solid-state reaction

Sr₅(PO₄)₂SiO₄:Eu²⁺ phosphosilicate phosphor was prepared by high temperature solid-state reaction. Effects of strontium sources (strontium oxide, strontium nitrate and strontium carbonate) and of phosphorus sources (diammonium phosphate, strontium monophosphate) on the reactivity of their mixture during heating and on phase composition, morphology and photoluminescence excitation and emission properties of the phosphors were investigated by TG–DTG–DSC, XRD, SEM and photoluminescence spectroscopy. The sequence of the solid-state reactions when using the different starting reagents was discussed based on the TG–DTG–DSC results. It was found that it is hard to prepare pure Sr₅(PO₄)₂SiO₄:Eu²⁺ phosphor with either of strontium sources studied when stoichiometric (NH₄)₂HPO₄ was used as a phosphorus source. Minor Sr₂SiO₄ impurity phase was present in the phosphors. The content of impurity phase, the morphology and resultant photoluminescence properties of the phosphors were markedly influenced by the strontium source employed. When SrCO₃ was used as the strontium source, the phase purity of the phosphor was improved with the addition of excess (NH₄)₂HPO₄. When (NH₄)₂HPO₄with 5% excess or SrHPO₄ in stoichiometric ratio was used as the phosphorus source a pure phase phosphor was obtained. In addition, the morphology and photoluminescence of the phosphor were also influenced by phosphorus source. The possible reasons causing different properties of the phosphors prepared using different raw materials were discussed based on reaction schemes.     

Surface-enhanced IR spectroscopy investigation on the electro-oxidation of CO adlayer at a polycrystalline Pt film electrode in Cl-containing HClO4

The electro-oxidation of CO adlayer on Pt electrode in Cl⁻-containing 0.1 M HClO₄ has been investigated with in situ attenuated-total-reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS). Two potentials were selected for predosing CO on the Pt electrode: one is in the H-UPD region, i.e., 0.1 V (vs. RHE) and the other is in the double-layer region, i.e., 0.45 V (vs. RHE). The broadening of the prewave and the main peak for the CO oxidation is observed, in addition to the positively shifted oxidation potentials. The spectroelectrochemical data suggest the specific adsorption of Cl⁻ starts at a potential as negative as 0.1 V which may compete with the adsorption of OH at CO-unoccupied sites (including but not limited to defect sites) and/or hinder the diffusion of CO to OH adsorption sites on Pt electrode, slowing down the CO oxidation. This competitive Cl⁻ adsorption at lower potentials disrupts the interfacial free H₂O structure on the top of CO adlayer, signaled by a reduced OH stretching band intensity.     

Kinetics of Polyurethane Formation in Polymerization Reactions Using the Organometallic Diol (η5-C5H4CH2CH2OH)2Mo2(CO)6

Summary The kinetics of the dibutyltin diacetate (DBTA) – catalyzed polymerization reactions of (η⁵-C₅H₄CH₂CH₂OH)₂Mo₂(CO)₆ with Hypol 2000 (an isocyanate-terminated polyether prepolymer) and with 1,4-butanediol were studied, as were the kinetics of a copolymerization involving (η⁵-C₅H₄CH₂CH₂OH)₂Mo₂(CO)₆ and PEG-1000 (a poly(ethylene glycol)) with Hypol 2000. The purpose was to determine if (η⁵-C₅H₄CH₂CH₂OH)₂Mo₂(CO)₆ appreciably affected the overall rate of the polymerization reaction and if it changed the mechanism of the reaction. The kinetics were analyzed with a fitting program, which allowed extraction of the rate constants for the individual elementary steps in the mechanism. The results showed that (η⁵-C₅H₄CH₂CH₂OH)₂Mo₂(CO)₆ does not significantly alter the timescale of the reaction and that the same reaction mechanism is likely used as with the 1,4-butanediol and PEG-1000. There are some differences in the rate constants of the elementary steps, but these differences can be attributed to the increased steric crowding caused by the bulkier (η⁵-C₅H₄CH₂CH₂OH)₂Mo₂(CO)₆ diol. The effect of the (η⁵-C₅H₄CH₂CH₂OH)₂Mo₂(CO)₆ on the polymers’ physical properties was also investigated. As is the case with other segmented polyurethanes, the hydrogen bonding index (HBI) and the relative amount of soft segments of the (η⁵-C₅H₄CH₂CH₂OH)₂Mo₂(CO)₆-containing polyurethane correlate in a general way with the physical properties of the polymer.     

The RuCl3(dppb)H2O complex: A new metal-assisted oxidative dehydrogenation of the o-phenylenediamine ligand

The trans-[RuCl₂(dppb)(bqdi)] and trans-[RuCl₂(dppb)(opda)] complexes (dppb = 1,4-bis(diphenylphosphine)butane, bqdi = o-benzoquinonediimine, and opda = o-phenylenediamine) were synthesized from the reaction of the mer-[RuCl₃(dppb)(H₂O)] aqua-complex with the opda ligand. The X-ray structural and electrochemical characterizations of the isolated compounds showed that this aqua-complex induces the oxidative dehydrogenation of the amine species (opda) to the imine form (bqdi) of the o-phenylene ligand during the synthetic procedure. In the presence of oxygen, the ³¹P{¹H} NMR experiments confirmed that the trans-[RuCl₂(dppb)(bqdi)] complex is the only product formed.     

Influence of the Type of Reducing Agent (H2, CO, C3H6 and C3H8) on the Reduction of Stored NOX in a Pt/BaO/Al2O3 Model Catalyst

In this investigation, a comparative study for a NO _X storage catalytic system was performed focusing on the parameters that affect the reduction by using different reductants (H₂, CO, C₃H₆ and C₃H₈) and different temperatures (350, 250 and 150 °C), for a Pt/BaO/Al₂O₃ catalyst. Transient experiments show that H₂ and CO are highly efficient reductants compared to C₃H₆ which is somewhat less efficient. H₂ shows a significant reduction effect at relatively low temperature (150 °C) but with a low storage capacity. We find that C₃H₈does not show any NO _X reduction ability for NO _X stored in Pt/BaO/Al₂O₃ at any of the temperatures. The formation of ammonia and nitrous oxide is also discussed.     

NMR study of temperature-induced phase separation and polymer-solvent interactions in poly(vinyl methyl ether)/D2O/ethanol solutions

The changes in the dynamic structure during temperature-induced phase transition in D₂O/ethanol solutions of poly(vinyl methyl ether) (PVME) were studied using NMR methods. The effect of polymer concentration and ethanol (EtOH) content in D₂O/EtOH mixtures on the appearance and extent of the phase separation was determined. Measurements of ¹H and ¹³C spin-spin and spin-lattice relaxations showed the presence of two kinds of EtOH molecules: besides the free EtOH expelled from the PVME mesoglobules there are also EtOH molecules bound in PVME mesoglobules. The existence of two different types of EtOH molecules at temperatures above the phase transition was in solutions with polymer concentration 20 wt% manifested by two well-resolved NMR signals (corresponding to free and bound EtOH) in ¹³C and ¹H NMR spectra. With time the originally bound EtOH is slowly released from globular-like structures. From the point of view of polymer-solvent interactions in the phase-separated PVME solutions both EtOH and water (HDO) molecules show a similar behaviour so indicating that the decisive factor in this behaviour is a polar character of these molecules and hydrogen bonding.     

H NMR study of temperature-induced phase transitions in D2O solutions of poly(N-isopropylmethacrylamide)/poly(N-isopropylacrylamide) mixtures and random copolymers

¹H NMR spectroscopy was used to investigate temperature-induced phase transitions in D₂O solutions of poly(N-isopropylmethacrylamide) (PIPMAm)/poly(N-isopropylacrylamide) (PIPAAm) mixtures and P(IPMAm/IPAAm) random copolymers of various composition on molecular level. While two phase transitions were detected for PIPMAm/PIPAAm mixtures, only single phase transition was found for P(IPMAm/IPAAm) copolymers. The phase transition temperatures of PIPAAm component (appears at lower temperatures) are not affected by the presence of PIPMAm in the mixtures; on the other hand, the temperatures of the phase transition of PIPMAm component (appears at higher temperatures) are affected by the phase separation of the PIPAAm component and depend on concentration of the solution. For P(IPMAm/IPAAm) random copolymers, a departure from the linear dependence of the transition temperatures on the copolymer composition was found for a sample with 75 mol% of IPMAm monomeric units.     

Separation of CO2/CH4 mixtures with the MIL-53(Al) metal–organic framework

Adsorptive separation of CH₄/CO₂ mixtures was studied using a fixed-bed packed with MIL-53(Al) MOF pellets. Such pellets of MIL-53(Al) were produced using a polyvinyl alcohol binder. As revealed by N₂ adsorption isotherms, the use of polyvinyl alcohol as binder results in a loss in overall capacity of 32%. Separations of binary mixtures in breakthrough experiments were successfully performed at pressures varying between 1 and 8 bar and different mixture compositions. The binary adsorption isotherms reveal a preferential adsorption of CO₂ compared to CH₄ over the whole pressure and concentration range. The separation selectivity was affected by total pressure; below 5 bar, a constant selectivity, with an average separation factor of about 7 was observed. Above 5 bar, the average separation factor decreases to about 4. The adsorption selectivity is affected by breathing of the framework and specific interaction of CO₂ with framework hydroxyl groups. CO₂ desorption can be realised by mild thermal treatment.