Structure-activity relationship of surfactant for preparing DMFC anodic catalyst

Three kinds of surfactants as stabilizer were applied to the preparation of electrocatalysts for direct methanol fuel cell (DMFC). The catalysts have been characterized by examining their catalytic activities, morphologies and particle sizes by means of cyclic voltammetry, chronoamperometry, X-ray diffraction and transmission electron microscopy (TEM). It is found that the surfactants with different structures have a significantly influence on the catalyst shape and activity. The catalysts prepared with non-ionic surfactants as the stabilizer show higher activity for direct oxidation of methanol. The structure-activity relationship (SAR) analysis has been explored and the effect of hydrophile-lipophile balance (HLB value) has also been discussed.

Chemical bonding and electronic structure of 4d-metal monocarbides

Bond distances, vibrational frequencies, dissociation energies, electron affinities, ionization potentials and dipole moments of the title molecules in neutral and charged ions were studied by use of density functional method. Ground states for each molecule were assigned. For neutral and cationic molecules, the bond distance decreases from YC (YC+) to RhC (RhC+), then increases, while for anionic molecules, the bond distance decreases from YC- to RuC-, then increases. Opposite trend was observed for vibrational frequency. The bond ionic character decreases from ZrC to PdC for neutral molecules. The bonding patterns are discussed and compared with the available studies.

Synthesis and characterization of ultrafine CeF3 nanoparticles modified by catanionic surfactant via a reverse micelles route

In this article, we firstly reported on the synthesis and characterization of ultratine CeF3 nanoparticles (NPs) modified by catanionic surfactant via a reverse micelles-based route. The catanionic surfactant PN was prepared by mixing the di(2-ethylhexyl) phosphoric acid (DEHPA) and primary amine (N1923) with 1:1 molar ratio. It exhibited a high surface activity and formed much small reverse micelles in comparison with its individual component (DEHPA or N1923). The PN reverse micelles were then used as templates to prepare ultrafine CeF3 NPs. The narrow distributed nanoparticles have an average diameter 1.8 nm. FTIR spectra indicated that there existed strong chemical interactions between nanoparticles and the adsorbed surfactants. The modification resulted in the FFIR peak position of P=O shifting to lower energy. Due to the effect of modification and small size, the CeF3 NPs showed a remarkable red shift of 54 mn in the fluorescence emission in comparison with that of bulk material and a red shift of 18 nm in contrast with that of the normal CeF3 NPs with an average diameter of 16 nm.

One-step polyelectrolyte-based route to well-dispersed gold nanoparticles: Synthesis and insight

Polyelectrolytes have been widely used as building blocks for the creation of thickness-controllable multilayer thin films in a layer-by-layer fashion, and also been used as flocculants or stabilizer of colloids. This paper reports novel finding that a kind of polyelectrolyte, polyamines, can facilely induce HAuCl4 to spontaneously form well-stabilized gold nanoparticles without the additional step of introducing a reducing reagent during the elevation of temperature, even at room temperature in some cases. The polymer chain-confined microenvironment and the acid-induced evolution of amide of such kind of polyelectrolyte solution play an important role in the nucleation and growth of gold nanoparticles. This method would not only be helpful to gain an insight into the formation of gold nanoparticles in polyelectrolyte systems, but also provide a novel and facile one-step polyelectrolyte-based synthetic route to polyelectrolyte protected gold nanoparticles in aqueous media for potential applications. More importantly, this strategy will be general to the preparation of other nanoparticles.

Assembly of multilayer films containing iron(III)- substituted Dawson-type heteropolyanions and its electrocatalytic properties: cyclic voltammetry, electrochemical impedance spectroscopy and UV-Vis spectrometry

Ultrathin multilayer films have been prepared by means of alternate adsorption of iron(Ill)-substituted heteropolytungstate anions and a cationic redox polymer on the 4-aminobenzoic acid modified glassy carbon electrode surface based on electrostatic layer-by-layer assembly. Cyclic voltammetry, electrochemical impedance spectroscopy and UV-Vis absorption spectrometry have been used to easily monitor the uniformity of thus-formed multilayer films. Especially, the electrochemical impedance spectroscopy is successfully used to monitor the multilayer deposition processes and is a very useful technique in the characterization of multilayer films because it provides valuable information about the interfacial impedance features. All these results reveal regular film growth with each layer adsorption. The resulting multilayer films can effectively catalyze the reduction of H2O2,NO2- and BrO3-.

Anion coordination and molecular assembly in C2-substituted thiamine-anion systems: effects of the anion and molecular conformation

The compounds (het)(PtCl6)2H(2)O 1, (het)(HgI4).H2O 2 (het = 2-(alpha-hydroxyethyl)thiamine) and (hpt)(Hg2Br6) 3 (hpt = 2-(alpha-hydroxypropyl)thiamine) have been prepared and structurally characterized by X-ray crystallography in order to study the influence of the anion and molecular conformation on the formation of supramolecular architectures that adsorb anionic species. Both het and hpt molecules adopt the usual S conformation for C2-substituted thiamine but differ from the F conformation for C2-free thiamine derivatives. Two types of characteristic ligand-anion complexation are observed, being of the forms C(6')-H...anion...thiazolium-ring (in 1 and 2) and N(4'1)-H...anion...thiazolium-ring (in 3). The reaction of het with PtCl62- or HgI42- gives a 1-D double-chain in 1, consisting of two hydrogen-bonded het chains, which are cross-linked by anions through hydrogen bonding and anion...aromatic-ring interactions, or a cationic 3-D framework in 2 formed by the stacking of hydrogen-bonded sheets with anion-and-water-filled channels. In the case of 3, hydrogen-bonded hpt dimers and HgBr62- anions form alternate cation-anion columns. A comparison with the cases of C2-free thiamine-anion complexes indicates that the change in molecular conformation results in novel supramolecular assemblies in 1 and 2 and an analogous architecture in 3, which also depends on the nature of the anions.

Multilayer assemblies consisting of tri-vanadium-substituted heteropolyanions and its electrocatalytic properties

We describe the controlled fabrication of ultrathin multilayer films consisting of tri-vanadium- substituted heteropolytungstate anions (denoted as P2W15V3) and a cationic polymer of quaternized poly (4-vinylpyridine) partially complexed with osmium bis(2,2'-bipyridine) (denoted as QPVP-Os) on the 4-aminobenzoic acid (4-ABA) modified glassy carbon electrode (GCE) surface based on layer-by-layer assembly. Cyclic voltammetry and UV-vis absorption spectrometry have been used to easily monitor the thickness and uniformity of thus-formed multilayer films. The V-centered redox reaction of P2W15V3 in the multilayer films can effectively catalyze the reduction of BrO3- and NO2-. The resulting P2W15V3/QPVP-Os multilayer film modified electrode behaves as a much promising electrochemical sensor because of the low overpotential for the catalytic reduction of BrO3- and NO2-, and the catalytic oxidation of ascorbic acid.

A temperature-dependent interaction of neutral red with calf thymus DNA

Neutral red (NR) is used as a probe to study the temperature and concentration dependent interaction of a cationic dye with nucleic acid. A temperature-dependent interaction of NR with calf thymus DNA (CT DNA) has been studied by differential pulse voltammetry (DPV), UV-Visible absorption, circular dichroism (CD) and fluorescence spectroscopy. The experimental results of increasing peak current, changes in the UV-Visible absorption and fluorescence spectra of NR and decreasing the induced circular dichroism (ICD) intensity show that (i) the binding mode of NR molecules is changed from intercalating into DNA base pairs to aggregating along the DNA double helix and (ii) the orientation of NR chromophore in DNA double helix is also changed with the temperature.

Strontium-based initiator system for ring-opening polymerization of cyclic esters

An amino isopropoxyl strontium (Sr-PO) initiator, which was prepared by the reaction of propylene oxide with liquid strontium ammoniate solution, was used to carry out the ring-opening polymerization (ROP) of cyclic esters to obtain aliphatic polyesters, such as poly(epsilon-caprolactone) (PCL) and poly(L-lactide) (PLLA). The Sr-PO initiator demonstrated an effective initiating activity for the ROP of epsilon-caprolactone (epsilon-CL) and L-lactide (LLA) under mild conditions and adjusted the molecular weight by the ratio of monomer to Sr-PO initiator. Block copolymer PCL-b-PLLA was prepared by sequential polymerization of epsilon-CL and LLA, which was demonstrated by H-1 NMR, C-13 NMR, and gel permeation chromatography. The chemical structure of Sr-PO initiator was confirmed by elemental analysis of Sr and N, H-1 NMR analysis of the end groups in epsilon-CL oligomer, and Fourier transform infrared (FTIR) spectroscopy. The end groups of PCL were hydroxyl and isopropoxycarbonyl, and FTIR spectroscopy showed the coordination between Sr-PO initiator and model monomer gamma-butyrolactone. These experimental facts indicated that the ROP of cyclic esters followed a coordination-insertion mechanism, and cyclic esters exclusively inserted into the Sr-O bond.

Synthesis, structure and ionic conductivity of La2/3-xLi3xMoO4

A series of compounds, La2/3 - xLi3xMoO4, were first prepared. Their structures are tetragonal scheelites with the cationic defects. The cell parameters a, c and values of c/a decrease with the increasing of the substitution amount (3x) of lithium ion. Cationic vacancies are getting more as Li+ concentration is lower. The diffusion of lithium ion is predominant. The concentration of charge carriers increases with increasing the substitution amount (3x) of lithium ion, meanwhile, the concentration of cationic vacancies decreases. The conductivity approaches the best when the substitution amount (3x) of lithium ion is about 0.3. The conductivity of La0.567Li0.3MoO4 is 6.5 x 10(-6) S . cm(-1) at room temperature.

Characterization of organic-inorganic multilayer films by cyclic voltammetry, UV-Vis spectrometry, X-ray photoelectron spectroscopy, small-angle X-ray diffraction and electrochemical impedance spectroscopy

We have employed several techniques, including cyclic voltammetry, UV-Vis spectrometry, small-angle X-ray diffraction, X-ray photoelectron spectroscopy and electrochemical impedance spectroscopy, to characterize the formation processes and interfacial features of ultrathin multilayer films of silicotungstate and a cationic redox polymer on cysteamine-coated Au electrodes self-assembled monolayers. All of these techniques confirm that the multilayer films are built up stepwise as well as uniformly in a layer-by-layer fashion. In particular, the electrochemical impedance spectroscopy is successfully used to monitor the multilayer deposition processes. It has been proved that the electrochemical impedance spectroscopy is a very useful technique in characterization of multilayer films because it provides valuable information about the interfacial impedance features.

Interactions of thiamine monophosphate (TMP) with one- and two-dimensional polymeric halogenomercurate anions. Crystal structures of (TMP)(Hg2Br5)center dot 0.5H(2)O and (TMP)(2)(Hg3I8)

An investigation into the interactions between thiamine monophosphate (TMP) and anions has resulted in the preparation and X-ray characterization of the compounds (TMP)(Hg2Br5).0.5H(2)O (1) and (TMP)(2)(Hg3I8) (2). In each compound the TMP molecule exists as a monovalent cation in the usual F conformation. The halogenomercurate anions occur in two-dimensional (2-D) network in 1 or one-dimensional (1-D) chain in 2. In both 1 and 2, the structures consist of alternating cationic sheets of the hydrogen-bonded TMP molecules and anionic sheets of the polymeric halogenomercurate anions. The TMP molecule binds to the polymeric anions through the characteristic 'anion bridge I', C(2)-H..X...pyrimidinium (X = Br in 1 and 1 in 2), and electrostatic interactions between electropositive S(1) and halogen atoms. The 'anion bridge II' of the type N(4'1)-H...X...thiazolium (X = phosphate group) plays a role in stabilizing the molecular conformation. The biological implication of the host-guest-like complexation between TMP and polymeric anions is discussed.

Synthesis and crystal structure of cyclopentylindene rare earth complex (C5H9C9H6)(3)SMCl-Li+ (THF)(4)

Rare earth complex (C5H9C9H6)(3)SmCl-Li+ (THF)(4)( I ) was synthesized by reacting anhydrous SmCl3 with two equivalents of C5H9C9H6Li. From mix-solvent of THF and hexane, red color single crystals were obtained. The crystal belongs to a cubic system, space group P2(1)3 with unit cell parameters a= b=c= 1. 754 0(2) nm, alpha=beta=gamma=90degrees, V=5. 396 4(11) nm(3), Z = 4. The ten-coordinated samarium atom is bonded to three cyclopentylindenyl rings and a chlorine atom to form the anionic part of the title complex, ring centroids and the chlorine atom form a tortured tetrahedron around samarium. In the cationic part, lithium atom coordinates to four oxygen atoms of THF molecules to form a normal tetrahedron. The Sm-C(within the same ring) distance varies from 0. 268 to 0. 299 nm.

Study on the kinetics of ferrocene derivatives in polymer electrolyte/electrode interface at microelectrode

Heterogeneous electron transfer rate constants (k(s)) and diffusion coefficients (D) of the ferrocene and its derivatives. in a new synthetic comb polymer solvent, poly(dimethylsiloxane-g-monomethylether polyethylene glycol) (SCP), and several other polymer solvents were estimated by using microelectrodes. Also, the influence of various supporting electrolytes on k(s) and D of ferrocene was studied. It was shown that k(s) and D of ferrocene decreased with increasing anionic size of the supporting electrolyte, but k(s) tended to increase with increasing radius of the solvated cation. Also, the cationic size of the supporting electrolytes had little effects on D. The values of k(s) and D for the ferrocene derivatives in the polymer solvents were in sharp contrast to those in monomeric solvents. Thus. the k(s) values were proportional to D in the polymer solvents. which indicates that solvent dynamics control of the electrode reaction. The values of k(s) and D of ferrocene in SCP were larger than those in other polymer solvents indicating that SCP is a good polymer solvent. (C) 2000 Elsevier Science B.V. All rights reserved.

Fabrication and electrochemical behaviors of multilayers composed of heteropholyanions and poly(diallyldimethylammonium chloride) on 4-aminothiophenol modified gold electrodes

Multilayer films composed of heteropolyanions (HPAS, SiMo11 VO405-) and cationic polymer poly(diallyldimethylammonium chloride) on 4-aminothiophenol self-assembled-monolayer were fabricated by electrochemical growth. Growth processes of the composite films were characterized by cyclic voltammetry. The results prove the third redox peak of Mo increases more rapidly, otherwise the other Mo redox peaks increase very slowly when the number of layers of heteropolyanions is greater. The peak potentials of composite films shift linearly to negative position with higher pH, which implies that protons are involved in the redox processes of HPA. The investigation of electrocatalytic behaviors of composite films shows a good catalytic activity for the reductions of HNO2 and BrO3-. Catalytic currents increase with increasing number of layers of heteropolyanions, moreover, the catalytic currents have a good linear relationship with the concentrations of BrO3-.