Direct evidence of oxidized gold on supported gold catalysts

Supported gold catalysts have drawn worldwide interest due to the novel properties and potential applications in industries. However, the origin of the catalytic activity in gold nanoparticles is still not well understood. In this study, time-of-flight secondary ion mass spectroscopy (TOF-SIMS) has been applied to investigate the nature of gold in Au (1.3 wt %)/gamma-Al2O3 and Au (2.8 wt %)/TiO2 catalysts prepared by the deposition-precipitation method. The SIMS spectrum of the supported gold catalysts presented AuO-, AuO2-, and AuOH- ion clusters. These measurements show direct evidence for oxidized gold on supported gold catalysts and may be helpful to gaining better understanding of the origin of the catalytic activity.     

Calorimetric and thermal decomposition kinetic study of Tb(Tyr)(Gly)<Subscript>3</Subscript>Cl<Subscript>3</Subscript>·3H<Subscript>2</Subscript>O

The solid-state ternary complex of terbium chloride with L-tyrosine and glycine, [Tb(Tyr)(Gly)₃Cl₃·3H₂O], was synthesized and characterized. Using a solution-reaction isoperibol calorimeter, the enthalpy of reaction for the following reaction, TbCl₃·6H₂O(s)+Tyr(s)+3Gly(s)=Tb(Tyr)(Gly)₃Cl₃·3H₂O(s)+3H₂O(l), was determined to be (5.1±0.6) kJ mol^-1. The standard enthalpy of formation of Tb(Tyr)(Gly)₃Cl₃-3H₂O at T=298.15 K has been derived as -(4267.3±2.3) kJ mol^-1. The thermal decomposition kinetics of the complex was studied by non-isothermal thermogravimetry in the temperature range of 325-675 K. Two main mass loss stages existed in the process of the decomposition of the complex, the kinetic parameters for the second stage were analyzed by means of differential and integral methods, respectively. Comparing the results of differential and integral methods, mechanism functions of the thermal decomposition reaction for its second stage were proposed. The kinetic equation can be expressed as: d/dt=Aexp(-E/RT)(1-)². The average values of the apparent activation energy E and pre-exponential factor A were 213.18 kJ mol^-1 and 2.51·10²⁰ s^-1, respectively.     

Standard enthalpy of formation of 3,4,5-trimethoxybenzoic acid

The energy of combustion of crystalline 3,4,5-trimethoxybenzoic acid in oxygen at T=298.15 K was determined to be -4795.9±1.3 kJ mol^-1 using combustion calorimetry. The derived standard molar enthalpies of formation of 3,4,5-trimethoxybenzoic acid in crystalline and gaseous states at T=298.15 K, Δ_fH_m ^Θ (cr) and Δ_fH_m ^Θ (g), were -852.9±1.9 and -721.7±2.0 kJ mol^-1, respectively. The reliability of the results obtained was commented upon and compared with literature values. This revised version was published online in August 2006 with corrections to the Cover Date.     

Synthesis, structure, spectroscopic properties, and electrochemistry of (1,8,15,22-tetrasubstituted phthalocyaninato)lead complexes

Three (1,8,15,22-tetrasubstituted phthalocyaninato)lead complexes Pb[Pc(alpha-OR)(4)] [H(2)Pc(alpha-OC(5)H(11))(4) = 1,8,15,22-tetrakis(3-pentyloxy)phthalocyanine; H(2)Pc(alpha-OC(7)H(15))(4) = 1,8,15,22-tetrakis(2,4-dimethyl-3-pentyloxy)phthalocyanine; H(2)Pc(alpha-OC(10)H(7))(4) = 1,8,15,22-tetrakis(2-naphthyloxy)phthalocyanine] (1-3) have been prepared as racemic mixtures by treating the corresponding metal-free phthalocyanines H(2)Pc(alpha-OR)(4) (4-6) with Pb(OAc)(2).3H(2)O in refluxing n-pentanol. The molecular structure of Pb[Pc(alpha-OC(5)H(11))(4)] (1) in the solid state has been determined by single-crystal X-ray diffraction analysis. This compound, having a nonplanar structure, crystallizes in the monoclinic system with a P2(1)/c space group. Each unit cell contains two pairs of enantiomeric molecules, which are linked by weak coordination of the Pb atom of one molecule with an aza nitrogen atom and its neighboring oxygen atom from the alkoxy substituent of another molecule, forming a pseudo-double-decker supramolecular structure in the crystals with a short ring-to-ring separation, 2.726 A, and thus a strong ring-ring pi-pi interaction. The decreased molecular symmetry for these complexes has also been revealed by the NMR spectra of 1 and 2. The methyl protons of the 3-pentyloxy and 2,4-dimethyl-3-pentyloxy side chains of 1 and 2, respectively, are chemically inequivalent. In addition to the elemental analysis and various spectroscopic characterizations, these compounds have also been electrochemically studied. Two one-electron oxidations and up to five one-electron reductions have been revealed by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) methods.     

An unprecedented 8-fold interpenetrating diamondoid-like coordination polymer containing a Cu+(4)(RCO2)(4) cluster as connecting node

The reaction of Cu(I)(CH(3)CN)(4)BF(4) with 4-pyridylacrylic acid (4-HPYA) affords an unprecedented 8-fold interpenetrating diamondoid-like coordination polymer network [Cu(I)(3)(4-PYA)(2)(H(2)O)(BF(4)) ] (1) with a Cu(+)(4)(CO(2))(4) cluster as connecting node. The interpenetration in metal coordination polymers is the highest degree ever found within diamondoid nets containing a cluster as connecting note. Its fluorescent property was also reported.     

Low‐Temperature Facile Template Synthesis of Crystalline Inorganic Composite Hollow Spheres

This report presents a facile approach for the low‐temperature synthesis of crystalline inorganic‐oxide composite hollow spheres by employing the bulk controlled synthesis of inorganic‐oxide nanocrystals with polymer spheres as templates. The sulfonated polystyrene gel layer can adsorb the target precursor and induce inorganic nanocrystals to grow on the template in situ. The crystalline phase and morphology of the composite shell is tunable. By simply adjusting the acidity of the titania sol, crystalline titania composite hollow spheres with tunable crystalline phases of anatase, rutile, or a mixture of both were achieved. The approach is general and has been extended to synthesize the representative perovskite oxide (barium and strontium titanate) composite hollow spheres. The traditional thermal treatment for crystallite transformation is not required, thus intact shells can be guaranteed. The combination of oxide properties such as high refractive index, high dielectric constant, and catalytic ability with the cavity of the hollow spheres is promising for applications such as opacifiers, photonic crystals, high‐κ‐gate dielectrics, and photocatalysis.     

A chelating resin containing S, N and O atoms: Synthesis and adsorption properties for Hg(II)

A novel chelating resin containing S, N and O atoms (PSME-EDA) was synthesized by using poly(2-hydroxyethylmercaptomethylstyrene) (PSME) and diethanolamine (EDA) as materials. Its structure was characterized by elemental analysis, Fourier transform-infrared spectra (FTIR), scanning electron microscopy (SEM) and X-ray diffraction (XRD). The adsorption of the resin for Hg²⁺ was investigated. The saturated adsorption capacity of PSME-EDA for Hg²⁺ could reach to about 1.1 mmol/g at 25 °C when the initial Hg²⁺ concentration was 0.02 mol/l. Some factors affecting the adsorption such as temperature, reaction time and ion concentration were also studied. The results showed that adsorption was controlled by liquid film diffusion. The increasing of temperature was beneficial to adsorption. The Langmuir model was better than the Freundlich model to describe the isothermal process. The values of ΔG, ΔH, and ΔS calculated at 25 °C were −7.99 kJ mol⁻¹, 22.5 kJ mol⁻¹ and 34.4 J mol⁻¹ K⁻¹, respectively. The adsorption mechanism of PSME-EDA resin for Hg(II) was confirmed by X-ray photoelectron spectroscopy (XPS).     

Packing capilllary electrochromatography columns using vacuum--a preliminary study

This paper introducesa novel method for packing Capillary Electrochromatography Columns (CEC). Using vacuum packing methodology, silica particles as small as 1 microm were successfully packed into the capillary columns with 75 microm inner diameter. The columns are verystable and show no noticeable loss in efficiency after 200 sample injections. The performance of these vacuum packed capillary columns was evaluated with a mixture of aromatic and non-aromatic compounds. A 24 cm long capillary column can produce peak efficiencies of around 45,000 plates for benzene.     

Electrochemical studies of NiTMpyP and interaction with DNA

In this paper, cyclic voltammetry, linear sweep voltammetry and chronocoulometry in connection with the hang mercury drop electrode were used to study NiTMpyP and its mixture with DNA. The reduction of NiTMpyP in our experimental conditions involves in 4e reduction of TMpyP. NiTMpyP interacting with DNA forms electrochemically non-active complex DNA-2NiTMpyP, which can not be reduced on the Hg electrode. The peak potential of NiTMpyP does not shift and its electrochemical kinetic parameters indicate no significant change in the presence of DNA. However, the reduction current of NiTMpyP decreases obviously due to the formation of DNA-2NiTMpyP, which implies its equilibrium concentration decreases when DNA was mixed. The decrease of peak current is proportional to DNA concentration, which can be applied to estimate DNA concentration.