Facile synthesis of thiol-functionalized amphiphilic polylactide–methacrylic diblock copolymers

Biodegradable amphiphilic diblock copolymers based on an aliphatic ester block and various hydrophilic methacrylic monomers were synthesized using a novel hydroxyl-functionalized trithiocarbonate-based chain transfer agent. One protocol involved the one-pot simultaneous ring-opening polymerization (ROP) of the biodegradable monomer (3S)-cis-3,6-dimethyl-1,4-dioxane-2,5-dione (L-lactide, LA) and reversible addition–fragmentation chain transfer (RAFT) polymerization of 2-(dimethylamino)ethyl methacrylate (DMA) or oligo(ethylene glycol) methacrylate (OEGMA) monomer, with 4-dimethylaminopyridine being used as the ROP catalyst and 2,2′-azobis(isobutyronitrile) as the initiator for the RAFT polymerization. Alternatively, a two-step protocol involving the initial polymerization of LA followed by the polymerization of DMA, glycerol monomethacrylate or 2-(methacryloyloxy)ethyl phosphorylcholine using 4,4′-azobis(4-cyanovaleric acid) as a RAFT initiator was also explored. Using a solvent switch processing step, these amphiphilic diblock copolymers self-assemble in dilute aqueous solution. Their self-assembly provides various copolymer morphologies depending on the block compositions, as judged by transmission electron microscopy and dynamic light scattering. Two novel disulfide-functionalized PLA-branched block copolymers were also synthesized using simultaneous ROP of LA and RAFT copolymerization of OEGMA or DMA with a disulfide-based dimethacrylate. The disulfide bonds were reductively cleaved using tributyl phosphine to generate reactive thiol groups. Thiol–ene chemistry was utilized for further derivatization with thiol-based biologically important molecules and heavy metals for tissue engineering or bioimaging applications, respectively.

Potassium-doped Ni-MgO-ZrO catalysts for dry reforming of methane to synthesis gas

Ni/K-MgO-ZrO catalysts for dry reforming of methane, with a range of Mg/Zr ratios and each containing about 10 wt% Ni, were prepared via Ni nitrate impregnation on MgO-ZrO supports synthesized by co-precipitation using KCO. It was found that a proportion of the potassium of the precipitant remained in the samples and improved the stability of the catalysts in the reaction. It was also shown that reduction of the catalysts at 1,023 K without calcination in air is necessary for stable and high activity; calcination in air at 1,073 K gives a deterioration of the catalytic properties, leading to rapid deactivation during the reaction. The order of the CH conversions of the reduced catalysts after 14 h on stream was as follows: Ni/K-MgZr ~ Ni/K-Mg ≥ Ni/K-MgZr Ni/K-Zr. A catalyst with 0.95 wt% K on MgO-ZrO with a Mg:Zr mole ratio of 5:2 showed the best resistance to deactivation. Experiments in a microbalance system showed that there was only negligible coke deposition on the surface of this sample. This behaviour was attributed to the presence of Ni nanoparticles with a diameter of less than 10 nm located on a MgO/NiO solid solution shell doped by K ions; this in turn covers a core of tetragonal ZrO and/or a MgO/ZrO solid solution. This conclusion was supported by EDS/TEM, XPS, XRD and H chemisorption measurements. © 2013 Springer Science+Business Media New York.

Application of heterogeneous catalysts prepared by mechanochemical synthesis

Mechanochemical synthesis has the potential to provide more sustainable preparative routes to catalysts than the current multistep solvent-based routes. In this review, the mechanochemical synthesis of catalysts is discussed, with emphasis placed on catalysts for environmental, energy and chemical synthesis applications. This includes the formation of mixed-metal oxides as well as the process of dispersing metals onto solid supports. In most cases the process involves no solvent. Encouragingly, there are several examples where the process is advantageous compared with the more normal solvent-based methods. This can be because of process cost or simplicity, or, notably, where it provides more active/selective catalysts than those made by conventional wet chemical methods. The need for greater, and more systematic, exploration of this currently unconventional approach to catalyst synthesis is highlighted.

Low loading platinum nanoparticles on reduced graphene oxide-supported tungsten carbide crystallites as a highly active electrocatalyst for methanol oxidation

In this study, low loading platinum nanoparticles (Pt NPs) have been highly dispersed on reduced graphene oxide-supported WC nanocrystallites (Pt-WC/RGO) via program-controlled reduction-carburization technique and microwave-assisted method. The scanning electron microscopy and transmission electron microscopy results show that WC nanocrystallites are homogeneously decorated on RGO, and Pt NPs with a size of ca. 3 nm are dispersed on both RGO and WC. The prepared Pt-WC/RGO is used as an electrocatalyst for methanol oxidation reaction (MOR). Compared with the Pt/RGO, commercial carbon-supported Pt (Pt/C) and PtRu alloy (PtRu/C) electrocatalysts, the Pt-WC/RGO composites demonstrate higher electrochemical active surface area and excellent electrocatalytic activity toward the methanol oxidation, such as better tolerance toward CO, higher peak current density, lower onset potential and long-term stability, which could be attributed to the characterized RGO support, highly dispersed Pt NPs and WC nanocrystallites and the valid synergistic effect resulted from the increased interface between WC and Pt. The present work proves that Pt-WC/RGO composites could be a promising alternative catalyst for direct methanol fuel cells where WC plays the important role as a functional additive in preparing Pt-based catalysts because of its CO tolerance and lower price. 

Effect of methanol concentration on oxygen reduction reaction activity of Pt/C catalysts

The oxygen reduction reaction (ORR) activity of Pt/C catalysts was investigated in electrolytes of 0.5 mol/L H2SO4 containing varying concentrations of methanol in a half-cell. It was found that the ORR activity was improved notably in an electrolyte of 0.5 mol/L H2SO4 containing 0.1 mol/L CH3OH as compared with that in 0.5 mol/L H2SO4, 0.5 mol/L H2SO4 containing 0.5 mol/L CH3OH, or 0.5 mol/L H2SO4 containing 1.0 mol/L CH3OH electrolytes. The same tendency for improved ORR activity was also apparent after commercial Nafion (R) NRE-212 membrane was hot-pressed onto the catalyst layers. The linear sweep voltammetry results indicate that the ORR activities of the Pt/C catalyst were almost identical in the 0.5 mol/L H2SO4 + 0.1 mol/L CH3OH solution before and after coated with the Nafion (R) membrane. Electrochemical impedance spectroscopy results demonstrated that the resistance of the Nafion (R) membrane is smaller in the electrolyte of 0.5 mol/L H2SO4 + 0.1 mol/L CH3OH than in other electrolytes with oxygen gas feed. This exceptional property of the Nafion (R) membrane is worth investigating and can be applied in fuel cell stacks to improve the system performance. (c) 2013, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

RuxNb1-xO2 catalyst for the oxygen evolution reaction in proton exchange membrane water electrolysers

Bimetallic catalyst system of ruthenium oxide (RuO) and niobium oxide (NbO) was prepared using the Adams method and the hydrolysis method. Physical and electrochemical characterizations of the catalysts were studied using X-ray diffraction (XRD), Scanning electron microscopy (SEM), cyclic voltammogram (CV) and polarization measurements. NbO addition to RuO was found to increase the stability of RuO. In Adams method the sodium nitrate was found to be forming complex with NbO at high temperature reaction. This makes Adams method unsuitable for the synthesis of RuO -NbO bimetallic system. Hydrolysis method on other hand does not have this problem. But a proper mixture of two oxides was not obtained in hydrolysis method. A lower crystallite size for bimetallic system was obtained with Adams method compared to hydrolysis method. RuO prepared by Adams method had higher activity compared to the hydrolysis counterpart in electrolyzer operation with nafion membrane. A cell voltage of 1.62 V was obtained with RuO (A) at 1 A/cm. A higher stability for RuNbO(A) compared to RuO(A) was observed in continuous cyclic voltammogram and electrolyzer cell test. Copyright © 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Investigating the promotional effect of methanol on the low temperature SCR reaction on Ag/Al2O3

Methanol has been shown to promote the hydrocarbon selective catalytic reduction of NO with octane and toluene over 2wt% Ag/AlO catalyst for the first time. In order to understand its role in the reaction fast transient kinetic methods and in situ DRIFTS analysis have been used. The catalytic activity tests showed that the addition of methanol to the HC-SCR reaction results in a significant improvement in the low temperature activity of a Ag/AlO catalyst, despite the fact that methanol on its own is not reactive for the HC-SCR reaction. This promotional effect of methanol is dependent on the concentration of added methanol and is not necessarily associated with a higher concentration of reductant in the SCR feed. The fast transient kinetic analysis has shown that at each temperature the addition of methanol enhances the conversions of both NO and octane and the production of N with high selectivity in comparison with those observed with n-octane or toluene alone. This phenomenon is similar to the effect of H which may be associated with the release of hydrogen and ammonia during the transient switches at 250 and 300°C. Together with the fast transient experiments, the DRIFTS results showed that NCO species are formed when introducing methanol to the n-octane-SCR feed while CN species are removed/consumed from the surfaces of the Ag catalyst. These NCO species formed by adding methanol may play a vital role in promoting the catalytic activity of NO reduction and methanol itself can be an in situ source for hydrogen formation, which subsequently enhances the SCR reaction. © 2014 Elsevier B.V.

One-pot two-step mechanochemical synthesis: ligand and complex preparation without isolating intermediates

Although the use of ball milling to induce reactions between solids (mechanochemical synthesis) can provide lower-waste routes to chemical products by avoiding solvent during the reaction, there are further potential advantages in using one-pot multistep syntheses to avoid the use of bulk solvents for the purification of intermediates. We report here two-step syntheses involving formation of salen-type ligands from diamines and hydroxyaldehydes followed directly by reactions with metal salts to provide the corresponding metal complexes. Five salen-type ligands 2,2'-[1,2-ethanediylbis[(E)-nitrilomethylidyne]] bisphenol, ` salenH2', 1; 2,2'-[(+/-)-1,2-cyclohexanediylbis-[(E)-nitrilomethylidyne]] bis-phenol, 2; 2,2'-[1,2-phenylenebis( nitrilomethylidyne)]-bis-phenol, ` salphenH2' 3; 2-[[(2-aminophenyl) imino] methyl]-phenol, 4; 2,2'-[(+/-)-1,2-cyclohexanediylbis[(E)-nitrilomethylidyne]]-bis[4,6-bis(1,1-dimethylethyl)]-phenol, ` Jacobsen ligand', 5) were found to form readily in a shaker-type ball mill at 0.5 to 3 g scale from their corresponding diamine and aldehyde precursors. Although in some cases both starting materials were liquids, ball milling was still necessary to drive those reactions to completion because precipitation of the product and or intermediates rapidly gave in thick pastes which could not be stirred conventionally. The only ligand which required the addition of solvent was the Jacobsen ligand 5 which required 1.75 mol equivalents of methanol to go to completion. Ligands 1-5 were thus obtained directly in 30-60 minutes in their hydrated forms, due to the presence of water by-product, as free-flowing yellow powders which could be dried by heating to give analytically pure products. The one-armed salphen ligand 4 could also be obtained selectively by changing the reaction stoichiometry to 1 : 1. SalenH(2) 1 was explored for the onepot two-step synthesis of metal complexes. In particular, after in situ formation of the ligand by ball milling, metal salts (ZnO, Ni(OAc)2 center dot 4H(2)O or Cu(OAc)(2)center dot H2O) were added directly to the jar and milling continued for a further 30 minutes. Small amounts of methanol (0.4-1.1 mol equivalents) were needed for these reactions to run to completion. The corresponding metal complexes [M(salen)] (M = Zn, 6; Ni, 7; or Cu, 8) were thus obtained quantitatively after 30 minutes in hydrated form, and could be heated briefly to give analytically pure dehydrated products. The all-at-once ` tandem' synthesis of [Zn(salen)] 6 was also explored by milling ZnO, ethylene diamine and salicylaldehyde together in the appropriate mole ratio for 60 minutes. This approach also gave the target complex selectively with no solvent needing to be added. Overall, these syntheses were found to be highly efficient in terms of time and the in avoidance of bulk solvent both during the reaction and for the isolation of intermediates. The work demonstrates the applicability of mechanochemical synthesis to one-pot multi-step strategies.

Synthesis of , of α,β-unsaturated aldehydes and nitriles via cross-metathesis reactions using Grubbs’ catalysts

A series of alpha,beta-unsaturated aldehydes and nitriles of significant interest in the fragrance industry have been prepared using Grubbs' catalysts in cross-metathesis reactions of electron-deficient olefins (i.e., acrolein, crotonaldehyde, methacrolein, and acrylonitrile) with various 1-alkenes, including 1-decene, 1-octene, 1-hexene and 2-allyloxy-6-methylheptane. The latter is of particular interest, as it has not previously being used as a substrate in cross-metathesis reactions and allows access to valuable intermediates for the synthesis of new fragrances. Most reactions gave good selectivity of the desired CM product (>= 90%). Detailed optimisation and mechanistic studies have been performed on the cross-metathesis of acrolein with 1-decene. Recycling of the catalyst has been attempted using ionic liquids. 

WC/CNT, WC/CNT/Pt Composite Material and Preparation Process Therefor and Use Thereof. (International Patent)

(EN)Disclosed are a WC/CNT， WC/CNT/Pt composite material and a preparation process therefor and use thereof. The WC/CNT/Pt composite material comprises mesoporous spherical tungsten carbide with a diameter of 1-5 microns, carbon nanotubes and platinum nano particles, with the carbon nanotubes growing on the surface of the mesoporous spherical tungsten carbide and expanding outward, and the platinum nano particles growing on the surfaces of the mesoporous spherical tungsten carbide and carbon nanotubes. The WC/CNT composite material comprises mesoporous spherical tungsten carbide with a diameter of 1-5 microns, and carbon nanotubes, with the carbon nanotubes growing on the surface of the mesoporous spherical tungsten carbide and expanding outward. The WC/CNT/Pt composite material of the present invention can be used as an electro-catalyst in a methanol flue battery, significantly improving the catalytic conversion rate and the service life of the catalyst. The WC/CNT composite material can be used as an electro-catalyst in the electro-reduction of a nitro aromatic compound, significantly improving the efficiency of organic electro-synthesis.

WC/CNT, WC/CNT/Pt Composite Material and Preparation Process Therefor and Use Thereof. (US patent)

Disclosed are a WC/CNT， WC/CNT/Pt composite material and a preparation process therefor and use thereof. The WC/CNT/Pt composite material comprises mesoporous spherical tungsten carbide with a diameter of 1-5 microns, carbon nanotubes and platinum nano particles, with the carbon nanotubes growing on the surface of the mesoporous spherical tungsten carbide and expanding outward, and the platinum nano particles growing on the surfaces of the mesoporous spherical tungsten carbide and carbon nanotubes. The WC/CNT composite material comprises mesoporous spherical tungsten carbide with a diameter of 1-5 microns, and carbon nanotubes, with the carbon nanotubes growing on the surface of the mesoporous spherical tungsten carbide and expanding outward. The WC/CNT/Pt composite material of the present invention can be used as an electro-catalyst in a methanol flue battery, significantly improving the catalytic conversion rate and the service life of the catalyst. The WC/CNT composite material can be used as an electro-catalyst in the electro-reduction of a nitro aromatic compound, significantly improving the efficiency of organic electro-synthesis.

THE SYNTHESIS OF BRIDGED-RING CARBOCYCLES AND HETEROCYCLES VIA PALLADIUM CATALYZED REGIOSPECIFIC CYCLIZATION REACTIONS

A catalyst system comprising 10 mol % (Pd(OAc) and 20 mol % PPh3 effects the cyclisation of aryl halides onto proximate alkenes via 5-, 6-, and 7-exo-trig, and 7-endo-trig processes giving a variety of bridged-ring carbo- and hetero-cycles in excellent yield. Double bond isomerisation in the product is rarely encountered and may be suppressed by the addition of Tl(1) salts. One example of diastereospecific bis-cyclisation is given and the crystal structure of 1-aza-2-sulphonyl-3,4-benzobicyclo[3.2.1]nona-6-ene is reported.

Some Understanding of Fischer-Tropsch Synthesis from Density Functional Theory Calculations

The combination of density functional theory (DFT) calculations and kinetic analyses is a very useful approach to study surface reactions in heterogeneous catalysis. The present paper reviews some recent work applying this approach to Fischer-Tropsch (FT) synthesis. Emphasis is placed on the following fundamental issues in FT synthesis: (i) reactive sites for both hydrogenation and C-C coupling reactions; (ii) reaction mechanisms including carbene mechanism, CO-insertion mechanism and hydroxyl-carbene mechanism; (iii) selectivity with a focus on CH(4) selectivity, alpha-olefin selectivity and chain growth probability; and (iv) activity.

Efficient and selective hydrogen peroxide-mediated oxidation of sulfides in batch and segmented and continuous flow using a peroxometalate-based polymer immobilised ionic liquid phase catalyst

The peroxometalate-based polymer immobilized ionic liquid phase catalyst [PO4{WO(O-2)(2)}(4)]@PIILP has been prepared by anion exchange of ring opening metathesis-derived pyrrolidinium-decorated norbornene/ cyclooctene copolymer and shown to be a remarkably efficient system for the selective oxidation of sulfides under mild conditions. A cartridge packed with a mixture of [PO4{WO(O-2)(2)}(4)]@PIILP and silica operated as a segmented or continuous flow process and gave good conversions and high selectivity for either sulfoxide (92% in methanol at 96% conversion for a residence time of 4 min) or sulfone (96% in acetonitrile at 96% conversion for a residence time of 15 min). The immobilized catalyst remained active for 8 h under continuous flow operation with a stable activity/selectivity profile that allowed 6.5 g of reactant to be processed (TON = 46 428) while a single catalyst cartridge could be used for the consecutive oxidation of multiple substrates giving activity-selectivity profiles that matched those obtained with fresh catalyst.

Liquid coordination complexes: a new class of Lewis acids as safer alternatives to BF3 in synthesis of polyalphaolefins

Liquid coordination complexes (LCCs) are a new class of liquid Lewis acids, prepared by combining an excess of a metal halide (e.g. GaCl3) with a basic donor molecule (e.g. amides, amines or phosphines). LCCs were used to catalyse oligomerisation of 1-decene to polyalphaolefins (PAOs). Molecular weight distribution and physical properties of the produced oils were compliant with those required for low viscosity synthetic (Group IV) lubricant base oils. Kinematic viscosities at 100 °C of ca. 4 or 6 cSt were obtained, along with viscosity indexes above 120 and pour points below −57 °C. In industry, to achieve similar properties, BF3 gas is used as a catalyst. LCCs are proposed as a safer and economically attractive alternative to BF3 gas for the production of polyalphaolefins.