Facile synthesis of platinum nanoelectrocatalyst with urchinlike morphology

A very simple and effective wet chemical route to direct synthesis of well-dispersed Pt nanoparticles with urchinlike morphology is proposed, which was carried out by simply mixing H2PtCl6 aqueous solution and poly(vinyl pyrrolidone) with the initial molar ratios of 1:3.5 kept constant at 30 degrees C for 3 days in the presence of formic acid. As-prepared urchinlike Pt nanostructures showed excellent electrocatalytic activity toward the reduction of dioxygen and oxidation of methanol and could be used as a promising nanoelectrocatalyst.

Double-template synthesis of platinum nanomaterials for oxygen reduction

Gas bubble dynamic template, a new green and promising template, can be used to prepare nanostructured materials with different shapes from electrochemical deposition processes. Different morphological platinum nanomaterials have been synthesized by the replacement reaction of the deposited copper nanomaterials which were obtained under negative potential along with H-2 evolution (dynamic template) at a glassy carbon electrode. Scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and electrochemical methods were adopted to characterize their structures and properties. The nanomaterials platinum exhibited excellent catalytic activity toward oxygen reduction. The results demonstrated that the strategy is a simple, cost-effective, and potent method to prepare platinum nanomaterials.

Synthesis and characterization of novel sulfonated polyimides from 1,4-bis(4-aminophenoxy)-naphthyl-2,7-disulfonic acid

A novel sulfonated diamine monomer, 1,4-bis(4-aminophenoxy)-naphthyl-2,7-disulfonic acid (BAPNDS), was synthesized. A series of sulfonated polyimide copolymers were prepared from BAPNDS, 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA) and nonsulfonated diamine 4,4'-diaminodiphenyl ether (ODA). Flexible, transparent, and mechanically strong membranes were obtained. The membranes displayed slightly anisotropic membrane swelling. The dimensional change in thickness direction was larger than that in planar. The novel SPI membranes showed higher conductivity, which was comparable or even higher than Nafion 117. Membranes exhibited methanol permeability from 0.24 x 10(-6) to 0.80 X 10(-6) cm(2)/s at room temperature, which was much lower than that of Nafion (2 x 10-6 CM2/s). The copolymers were thermally stable up to 340 degrees C. These preliminary results have proved its potential availability as proton-exchange membrane for PEMFCs or DMFCs.

Synthesis and properties of novel sulfonated polyimides containing binaphthyl groups as proton-exchange membranes for fuel cells

A novel sulfonated diamine monomer, 2,2'-bis(p-aminophenoxy)-1,1'-binaphthyl-6,6'-disulfonic acid (BNDADS), was synthesized. A series of sulfonated polyimide copolymers containing 30-80 mol % BNDADS as a hydrophilic component were prepared. The copolymers showed excellent solubility and good film-forming capability. Atomic force microscopy phase images clearly showed hydrophilic/hydrophobic microphase separation. The relationship between the proton conductivity and degree of sulfonation was examined. The sulfonated polyimide copolymer with 60 mol % BNDADS showed higher proton conductivity (0.0945-0.161 S/cm) at 20-80 degrees C in liquid water. The membranes exhibited methanol permeability from 9 x 10(-8) to 5 X 10(-7) cm(2)/s at 20 degrees C, which was much lower than that of Nafion (2 x 10(-6) cm(2)/s). The copolymers were thermally stable up to 300 degrees C. The sulfonated polyimide copolymers with 30-60 mol % BNDADS showed reasonable mechanical strength; for example, the maximum tensile strength at break of the sulfonated polyimide copolymer with 40 mol % BNDADS was 80.6 MPa under high moisture conditions. The optimum concentration of BNDADS was found to be 60 mol % from the viewpoint of proton conductivity, methanol permeability, and membrane stability.

The study of synthesis of poly(ethylene oxide)-b-poly(N,N-dimethylacrylamide) by atom transfer radical polymerization and self-assembly in selective solvents

Poly( ethylene oxide)-b-poly(N, N-dimethylacrylamide) (PEO-b-PDMA) was synthesized by successive atom transfer radical polymerization (ATRP) of N, N-dimethylacrylamide (DMA) monomer using PEO-Br macro initiators as initiator, CuBr and 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazamacrocyclotetra decane (Me-6[14] aneN(4)) as catalyst and ligand. PEO-Br macroinitiator was synthesized by esterification of PEO with 2-bromoisobutyryl bromide. GPC and H-1 NMR studies show that the plot of ln([DMA](0)/[ DMA]) against the reaction time is linear, and the molecular weight of the resulting PDMA increased linearly with the conversion. Within 3 h, the polymerization can reach almost 60% of conversion. PEO-b-PDMA copolymer with low polydispersity index (M-w/M-n approximate to 1.1) is obtained. Self-assembly of PEO-b-PDMA in selective solvents is also studied. It could self-assemble into micelles in methanol/acetone (1/10, v/v) solution. TEM analyses of the PEO-b-PDMA micelles with narrow size distribution revealed that their size and shape depend much on the copolymer composition.

Electrooxidation of methanol on carbon nanotubes supported Pt-Fe alloy electrode

The synthesis and characterization of catalysts based on bimetallic materials, Pt-Fe supported on multi-walled carbon nanotubes (MWNTs) for methanol electrooxidation is reported here. The catalyst was prepared by a spray-cooling process and characterized by TEM, EDS, ICP and XRD. The electrocatalytic properties of the Pt-Fe/MWNTs electrode for methanol oxidation have been investigated by cyclic voltammetry and chronoamperometry. It presented higher electrocatalytic activity and stability than a comparative Pt/ MWNTs catalyst. This may be attributed to the addition of Fe which leads to the small average particle size and high utilization of Pt in the Pt-Fe/MWNTs catalyst. The results imply that the Pt Fe/MWNTs composite has good potential applications in fuel cells.

Synthesis, crystal structure and magnetic properties of a chain coordination polymer {[Cu4L2(H2O)] center dot H2O}(n)

A chain coordination polymer with the chemical formula {[Cu4L2(H2O)] (.) H2O)(n), has been synthesized by the assembly reaction of K(2)CuL(.)1.5H(2)O and Cu(OAC)(2)(H2O)-H-. with a 1:1 mole ratio in methanol., where H4L=2-hydroxy-3-[(E)-({2-[(2-hydroxybenzoyl)imino]ethyl I imino)methyl] benzoic acid, OAC(-) = CH3COO-. The crystal structure was determined by single-crystal X-ray diffraction analysis, the compound has chain molecular structure formed by dissymmetrical tetranuclear units. The magnetic measurements showed that Cu-Cu of the complex exhibit antiferromagnetic interactions, and satisfactory fittings to the observed magnetic susceptibility data were obtained by assuming a binuclear system, and further using molecular field approximation to deal with magnetic exchange interactions between binuclear systems.

Synthesis, characterization and crystal structures of dibenzo-18-crown-6 sodium isopolytungstates

Two novel dibenzo-18-crown-6 sodium isopolytungstates, [(DB18C6)(CH3OH)Na](2)W(6)O(19)(.)DB18C6(.)H(2)O 1 and [(DB18C6)(DMF)(2)Na](4)W(10)O(32)(.)2DMF(.)2H(2)O 2, have been synthesized in mixed methanol and acetonitrile solvents and characterized by elemental analysis, TGA, IR and single crystal X-ray diffraction. The compound 1 crystallizes in the monoclinic space group C2/c with a = 23.182(8), b = 19.527(2), c = 18.737(3) Angstrom, beta = 115.15(2)degrees, V = 7678(3) Angstrom(3), Z = 4, and R1(wR2) = 0.0611(0.1504). The compound 2 crystallizes in the monoclinic space group P21/n with a = 16.516(2), b = 22.325(6), c = 20.425(7) Angstrom, beta = 91.78(2)degrees, V = 7528(3) Angstrom(3), Z = 2, and R1(wR2) = 0.0397(0.0773). The compound 1 exhibits a novel organic-inorganic sandwich-type structure, in which the crown ether-sodium complexes are coordinated to the terminal oxygen atoms of W6O192-. In compound 2, all Na+ ions are thoroughly enveloped into the organic moieties of crown ether and DMF molecules and are connected with the 'naked' polyanions W10O324- via the electrostatic attraction.

A new dinuclear molybdenum(V)-sulfur complex containing citrate ligand: synthesis and characterization of K2.5Na2NH4[Mo2O2S2(cit)(2)].5H(2)O

The complex, K2.5Na2NH4[Mo2O2S2(cit)(2)]. 5H(2)O (1), was obtained by crystallization from a solution of (NH4)(2)MoS4, potassium citrate (K(3)cit) and hydroxyl sodium in methanol and water under an atmosphere of pure nitrogen at ambient temperature. The crystals are triclinic, space group , a = 7.376 (3)Angstrom, b = 14.620 (2) Angstrom, c = 14.661 (1) Angstrom, alpha = 71.10 (1)degrees, beta = 81.77 (1)degrees, gamma = 78.27(2)degrees, R = 0.0584 for 2545 observed (I > 2 sigma (I)) reflections. Single crystal structure analysis reveals that citrate ligand coordinated to molybdenum atom through two carboxylato oxygens and one deprotonated hydroxyl oxygen together with two bridging sulfur atoms and a terminal oxygen atom completes distorted coordination octahedron around each molybdenum atom. Principal dimensions are: Mo = O-t, 1.707 Angstrom (av); Mo-S-b, 2.341 Angstrom (av); Mo-O-(hydroxyl), 2.021 Angstrom (av); Mo-O(alpha-carboxyl), 2.1290 Angstrom (av) and Mo-O(beta-carboxyl), 2.268(av) Angstrom. IR spectrum is in agreement with the structure.

Synthesis and miscibility studies of rodlike flexible polyimide molecular composites via para-para linked aromatic poly(amic ester) precursors

Para-para linked aromatic poly(amic ester) precursors of rodlike polyimide (PI) BPDA-PDA and polyetherimide (PEI) HQDPA-ODA were synthesized. The para-para linked poly(amic ester)s were employed in this work to obtain, in theory, full-imidized polyimides. The two precursors were mixed by dissolving them in N, N'-dimethyl acetamide and subsequently coagulating in methanol. After thermal imidization, the miscibility behaviour of the resulting composites has been studied by means of dynamic mechanical analysis (d.m.a.) and differential scanning calorimetry (d.s.c.). The composites show a single glass transition temperature (T-g) at both d.m.a. and d.s.c. in which the T-g increases with increasing PI content. These Tg values are reproducible in repeated heating cycles, suggesting the true miscibility of the blends. (C) 1997 Elsevier Science Ltd.

SYNTHESIS AND CHARACTERIZATION OF A NEW COMB-LIKE POLYMER-BASED ON POLY(VINYL METHYL ETHER-ALT-MALEIC ANHYDRIDE) BACKBONE

A new comblike polymer host for polymer electrolyte was synthesized by reacting monomethyl ether of poly(ethylene glycol) with poly(vinyl methyl ether-alt-maleic anhydride) and endcapping the residual carboxylic acid with methanol. Butanone was selected as a solvent for the esterification in order to obtain a completely soluble product. The synthesis process was traced through by LR. Compared with the model compounds, the presumed structure of this comblike polymer has been proved to be valid by C-13 NMR The comb polymer is a white rubbery solid. It can be dissolved in butanone and THF, and manifests good film forming ability.

New progress in R&D of lower olefin synthesis

This paper gives a brief review of R&D researches for light olefin synthesis directly and indirectly from synthesis gas in the Dalian Institute of Chemical Physics (DICP). The first pilot plant test was on methanol to olefin (MTO) reaction and was finished in 1993, which was based on ZSM-5-type catalyst and fixed bed reaction. In the meantime, a new indirect method designated as SDTO (syngas via dimethylether to olefin) was proposed. In this process, metal-acid bifunctional catalyst was applied for synthesis gas to dimethylether(DME) reaction, and modified SAPO-34 catalyst that was synthesized by a new low-cost method with optimal crystal size was used to convert DME to light olefin on a fluidized bed reactor. The pilot plant test on SDTO was performed and finished in 1995. Evaluation of the pilot plant data showed that 190-200 g of DME were yielded by single-pass for each standard cubic meter of synthesis gas. For the second reaction, 1.880 tons of DME or 2.615 tons of methanol produced 1 ton of light olefins, which constitutes of 0.533 ton of ethylene, 0.349 ton of propylene and 0.118 ton of butene. DICP also paid some attention on direct conversion of synthesis gas to light olefins. A semi-pilot plant test (catalyst 1.8 1) was finished in 1995 with a CO conversion > 70% and a C(2)(=)-C(4)(=) olefin selectivity 71-74% in 1000 h. (C) 2000 Published by Elsevier Science B.V. All rights reserved.

Methanol to olefin conversion catalysts

The past year has seen remarkable advances both in methanol to olefin process development and in understanding the catalysts and reactions invoked. The methanol to olefin process is now on the way to being commercialized locally with economic advantages in comparison with other natural gas utilization technologies and conventional naphtha cracking processes. Using a specially designed procedure, a catalyst for the selective synthesis of ethylene from methanol has been reliably reproduced. The relationships between catalyst properties and reaction performances are clearer than ever before.

Synthesis and spectroscopic investigation of iron(III) complexes of N'-(thioaroyl)pyridine-2-carbohydrazides

A new series of iron(III) complexes [Fe(L(1))(HL(1))], [Fe(L(1)) Cl]; [H2L(1) = N'-(2-methoxythiobenzoyl)pyridine-2-carbohydrazide], [Fe(L(2))(acac)], [Fe(HL(2))2 Cl]; [H2L(2) = N'-(4-methoxythiobenzoyl)pyridine-2-carbohydrazide] and [Fe(L(3)) (acac)]; [H2L(3) = N'-(2-hydroxythiobenzoyl)pyridine-2-carbohydrazide] were prepared by stirring/refluxing/mixing the respective ligand with FeCl3/Fe(acac)3 in chloroform/methanol. All the compounds were characterized by elemental analyses, magnetic susceptibility, IR, UV and Mossbauer spectral data. The complexes high/low spin state and have tetrahedral/octahedral geometry.

The application of calcined natural dolomitic rock as a solid base catalyst in triglyceride transesterification for biodiesel synthesis

Natural dolomitic rock has been investigated in the transesterification of C-4 and C-8 triglycerides and olive oil with a view to determining its viability as a solid base catalyst for use in biodiesel synthesis. XRD reveals that the dolomitic rock comprised 77% dolomite and 23% magnesian calcite. The generation of basic sites requires calcination at 900 degrees C, which increases the surface area and transforms the mineral into MgO nanocrystallites dispersed over CaO particles. Calcined dolomitic rock exhibits high activity towards the liquid phase transesterification of glyceryl tributyrate and trioctanoate, and even olive oil, with methanol for biodiesel production.