Organocatalytic Application of Direct Organo-Functionalized Mesoporous Catalysts Prepared by Microwave

The organic functional groups such as primary and quaternary amine, sulfonic acid, and amino acid, especially l-proline, have been tried to immobilize onto mesoporous materials by the direct synthesis method using microwave. Microwave induced direct functionalization enabled to get well ordered mesoporous structures and stable organic tethered groups with enhanced hydrothermal stability due to more hydrophobic surfaces as well as enhanced activity. The method is also useful for overcoming several shortcomings in the post-synthesis grafting method which suffers from pore blocking at the aperture, and difficulties in controlling the as obtained from the direct co-condensation method had their functional groups spatially loadings, as well as the dispersion of active sites. The organo-functionalized mesoporous silica dispersed on the surface which could play roles as single site catalysts. Direct tethering of organic functional groups was preferably synthesized by microwave, gave morphological control and illustrated superiority in some organocatalytic application such as Knoevenagel and Henry reactions base catalytic reaction, Claisen–Schmidt condensation, and diethyl malonate addition reactions.     

DME as Reductant for Continuous Lean Reduction of NO x over ZSM-5 Catalysts

Dimethyl ether (DME) is an interesting alternative fuel to diesel, but is not an efficient reductant in lean NO _x conversion over typical diesel HC-SCR catalysts. Comparatively high deNO _x activity was found over H-ZSM-5 in the presence of water, giving reduction of 28% NO and 37% NO₂ respectively with a DME/NO _x -ratio of 4.     

Novel Y2O3 Doped MnO x Binary Metal Oxides for NO x Storage at Low Temperature in Lean Burn Condition

MnO _x -Y₂O₃ binary metal oxide catalysts are synthesized by a constant-pH co-precipitation method, their ability of NO _x storage capacity and absorbing process were investigated. The pure MnO _x and Y₂O₃ calcined at 500 °C for 4 h in static air are both of body-centre structure, while the binary metal oxides containing Mn and Y are mainly of amorphous phase. The adulteration of Y₂O₃ can remarkably improve the specific surface areas of the catalysts, which probably result of the enhancement on NO storage capacity and catalytic oxidation ability of NO at 100 °C. The XPS results indicate that both Mn and Y have 3+ chemical states in the binary oxides. FT-IR spectra could be beneficial to explain the NO storage process on the binary metal oxide: NO can be adsorbed on the MnO _x and Y₂O₃ sites as nitrates and nitrites, respectively, and then the nitrites on Y₂O₃ site are shifted to Mn₂O₃ site and then is oxidized to nitrates. As a result, the NO storage capacity is enhanced due to the adulteration of Y₂O₃, finally the NO _x are adsorbed on the Mn₂O₃ site as nitrate species.     

Deposition of PtxRu1−x Catalysts for Methanol Oxidation in Micro Direct Methanol Fuel Cells

Platinum-ruthenium electrodes (Pt_xRu_1-x) have been prepared by electrochemical and electroless deposition and investigated as catalysts for the oxidation of methanol in acidic solutions. Pt_xRu_1-x deposits were electrochemically deposited from acidic chloride electrolytes at potentials between −0.46 and 0.34 V (vs. NHE). The composition of the electrodeposit was estimated by energy dispersive X-ray spectroscopy and is a strong function of the electrode potential. An empirical model for the deposition process is presented and kinetic parameters are estimated and discussed. Also, the methanol oxidation activity of the Pt_xRu_1-x catalysts was characterized by cyclic voltammetry in 1.0 M CH₃OH, 1.0 M H₂SO₄ solutions. Electroless Pt_xRu_1-x samples were prepared in a modified Leaman bath with hydrazine dihydrochloride as the reducing agent. The kinetic results for the electrochemical deposition of Pt_xRu_1-x were directly applied and the deposition potential was estimated as approximately 0.40 V.     

Synthesis of Nanostructured Titania Templated by Anionic Surfactant in Acidic Conditions

Nanostructured titania was synthesized by hydrolysis of titanium tetraisopropoxide (TTIP) in HCl acidic conditions using sodium dodecylsulfate (SDS) as the templating agent. The resultant SDS-titania composite solids were supposed to possess the lamellar nanostructure, which collapsed by calcination. The order of the nanostructure was improved with increasing the SDS/TTIP molar ratio. The nanostructure order also increased with the HCl/TTIP molar ratios, probably due to the enhanced attraction between the positively charged surfaces of titania clusters and the head groups of anionic surfactant. The calcined sample presented an advanced mesopore structure with uniform pore size and the surface area of ca. 200 m²/g, although the periodicity of the nanostructure was exceedingly reduced by the removal of the template. It is supposed that the mesopore structure did not result from the templated nanostructure, but was derived from the spaces between titania nano-sized particles closely arranged by the attraction with SDS molecular assemblies.     

The Distribution of Active ingredients in Supported Catalysts Prepared by Impregnation

Supported catalysts, one of the commonest forms of heterogeneous catalysts in practical use, consist of small crystallites of a catalytically active component dispersed in a porous support of high surface area. Impregnation of the support with an aqueous solution of a compound containing the appropriate catalytic component is an important and frequently used method of preparing this type of catalyst. A nonaqueous solution should be used if the sup port surface is hydrophobic or if hydrolysis of the support surface is to be avoided. In its simplest form, this impregnation method involves three steps: (1) contacting the support with impregnating solution for a certain period of time, (2) drying the support to remove the imbibed liquid, and (3) activating the catalyst by calcination, reduction, or other appropriate treatment.     

The Distribution of Active ingredients in Supported Catalysts Prepared by Impregnation

Supported catalysts, one of the commonest forms of heterogeneous catalysts in practical use, consist of small crystallites of a catalytically active component dispersed in a porous support of high surface area. Impregnation of the support with an aqueous solution of a compound containing the appropriate catalytic component is an important and frequently used method of preparing this type of catalyst. A nonaqueous solution should be used if the sup port surface is hydrophobic or if hydrolysis of the support surface is to be avoided. In its simplest form, this impregnation method involves three steps: (1) contacting the support with impregnating solution for a certain period of time, (2) drying the support to remove the imbibed liquid, and (3) activating the catalyst by calcination, reduction, or other appropriate treatment.     

Strong Size Effects in Supported Ionic Nanoparticles: Tailoring the Stability of NO x Storage Catalysts

Based on a well-defined model-catalyst approach, we study the particle size dependent properties of NO _x storage materials. The single-crystal based model systems are prepared on an ordered Al₂O₃ film, on which BaO nanoparticles are grown under ultrahigh-vacuum (UVH) conditions. Particle size and density are characterized by scanning tunneling microscopy (STM). The interaction with NO₂ is probed by molecular beam (MB) methods in combination with time-resolved IR reflection absorption spectroscopy (TR-IRAS). It is found that both, the stability and the formation kinetics of alumina supported barium nitrate nanoparticles show a strong dependence on particle size. Very small BaO particles are rapidly converted into nitrates, however, the resulting aggregates exhibit a strongly reduced thermal stability. Surface and bulk nitrate and nitrate features are identified by means of vibrational spectroscopy. It is concluded that the size dependencies are related to the formation and decomposition of surface-related BaNO _x species the decomposition temperature of which can be tuned over an exceptionally large temperature interval. It is suggested that the stability of these surface NO _x species is strongly modified by the underlying support.     

Investigation on Electrocatalytic Activity and Stability of Pt/C Catalyst Prepared by Facile Solvothermal Synthesis for Direct Methanol Fuel Cell

Pt nanoparticles supported on Vulcan XC‐72 carbon black have been synthesized by a facile solvothermal method. The obtained Pt/C catalysts are characterized by X‐ray diffraction (XRD), energy dispersive X‐ray analysis (EDAX), and transmission electron microscopy (TEM) analysis to identify Pt mean size and Pt content. The results of electrochemical measurements demonstrate that the Pt/C catalyst prepared at the reaction temperature of 140 °C and the reaction time of 2 h shows the biggest initial electrochemical area with an initial electrochemically active specific surface area (ESA) of 70.6 m²g_Pt⁻¹, the highest electrocatalytic stability with an ESA loss of 48.7% after 1,000 CV cycles, and the best electrocatalytic activity and stability toward methanol oxidation reaction (MOR) with a specific activity of 0.6 mA cm⁻² and a retention rate (the ratio of the final current density to the maximum current density) after 3,600 s of 42.8%. Moreover, the electrochemical performance of homemade Pt/C catalyst is superior to that of commercial Pt/C catalyst, suggesting that the solvothermal synthesis is a promising method for preparing Pt based catalyst.     

Efficient Reduction of NO x by H2 Under Oxygen-Rich Conditions over Pd/TiO2 Catalysts: An in situ DRIFTS Study

The H₂/NO/O₂ reaction under lean-burn conditions has been studied by means of in situ DRIFTS, reactor measurements and temperature-programmed desorption with the aim of understanding the very different behavior of Pd/TiO₂ and Pd/Al₂O₃ catalysts. The former deliver very high NO _x conversions (70-80%) with good N₂ selectivity whereas the latter show very low activity. In addition, PdTiO₂ exhibits two distinct NO _x reduction pathways, thus greatly extending the useful temperature range. It is shown that the PdTiO₂ low-temperature channel involves adsorption and subsequent dissociation of NO on reduced (Pd⁰) metal sites. The low activity of PdAl₂O₃ is a consequence of palladium remaining in an oxidized state under reaction conditions. The high-temperature NO reduction channel found with PdTiO₂ is associated with the generation and subsequent reaction of NH _x species.     

Effect of Preparation Conditions of Pt/C Catalysts on Oxygen Electrode Performance in Proton Exchange Membrane Fuel Cells

Supported Pt/C catalyst with 3.2 nm platinum crystallites was prepared by the impregnation—reduction method. The various preparation conditions, such as the reaction temperature, the concentration of precursor H₂PtCl₆ solution and the different reducing agents, and the relationship between the preparation conditions and the catalyst performance were studied. The carbon black support after heat treatment in N₂ showed improved platinum dispersion. The particle size and the degree of dispersion of Pt on the carbon black support were observed by transmission electron microscopy (TEM). The crystal phase composition of Pt in the catalyst was determined by X-ray diffraction (XRD). The surface characteristics of the carbon black support and the Pt/C catalyst were studied by X-ray photoelectron spectroscopy (XPS). The electrochemical characteristics of the Pt/C catalysts were evaluated from current—voltage curves of the membrane electrode assembly (MEA) in a proton exchange membrane fuel cell.     

Porous Polyimide Membranes Prepared by Wet Phase Inversion for Use in Low Dielectric Applications

A wet phase inversion process of polyamic acid (PAA) allowed fabrication of a porous membrane of polyimide (PI) with the combination of a low dielectric constant (1.7) and reasonable mechanical properties (Tensile strain: 8.04%, toughness: 3.4 MJ/m³, tensile stress: 39.17 MPa, and young modulus: 1.13 GPa), with further thermal imidization process of PAA. PAA was simply synthesized from purified pyromellitic dianhydride (PMDA) and 4,4-oxydianiline (ODA) in two different reaction solvents such as γ-butyrolactone (GBL) and N-methyl-2-pyrrolidinone (NMP), which produce M_w/PDI of 630,000/1.45 and 280,000/2.0, respectively. The porous PAA membrane was fabricated by the wet phase inversion process based on a solvent/non-solvent system via tailored composition between GBL and NMP. The porosity of PI, indicative of a low electric constant, decreased with increasing concentration of GBL, which was caused by sponge-like formation. However, due to interplay between the low electric constant (structural formation) and the mechanical properties, GBL was employed for further exploration, using toluene and acetone vs. DI-water as a coagulation media. Non-solvents influenced determination of the PAA membrane size and porosity. With this approach, insight into the interplay between dielectric properties and mechanical properties will inform a wide range of potential low-k material applications.     

Methane as Alternative in the Selective Reduction of NO over Supported Palladium Catalysts in Lean Conditions: Role of Redox Properties of Support Materials

The reduction of CH₄ by NO has been investigated in the presence of oxygen on palladium supported on alumina, ceria–zirconia mixed oxides and perovskite materials, mainly LaCoO₃. The activation procedure, under oxygen or hydrogen, drastically influences the catalytic performances of both catalysts. The stabilisation of a metallic or oxidic Pd phase leads to poor activity in the conversion of NO in the absence of oxygen. On the other hand, oxygen enhances the activity, particularly on the reduced Pd/LaCoO₃, in the CH₄ + NO reaction. Such results have been explained by different interactions between palladium and the support.     

High Strength and Barrier Properties of Biodegradable PPC/PBSA Blends Prepared by Reaction Compatibilization for Promising Application in Packaging

Poly(propylene carbonate) (PPC)/poly(butylene succinate-co-butylene adipate) (PBSA) blends are prepared via melt mixing using a twin-screw extruder. A one-step method based on the reaction compatibilization mechanism is used to prepare PPC/PBSA/AX8900(ethylene-methyl acrylate-glycidyl methacrylate random terpolymer) blends. The films of blends are prepared by an extrusion blown film machine. Fourier transform infrared spectroscopy results show that there is a strong hydrogen bonding between PPC and PBSA. The epoxy group of AX8900 can react with molecular chains of PPC and PBSA. It is shown from the rheological behavior that AX8900 can extend the molecular chains and increase the compatibility of PPC and PBSA. The films of PPC/PBSA blends exhibit more orientation structure than pure PPC film. The tensile strength of machine direction and transverse direction for 70PPC/30PBSA/1AX8900 film is higher than that for pure PPC film. The PPC/PBSA/AX8900 films have similar excellent barrier properties, compared with PPC film. The modified Maxwell theoretical model is used to predict and analyze changes in film barrier properties.     

High Performance Ion Exchange Membranes Prepared via Direct Polyacylation of Racemic and (S)‐1,1′‐Binaphthyl‐Based Cationic/Anionic Monomers

Side‐chain‐type sulfonated/quaternized aromatic polyelectrolytes with precisely controlled contents of ionized groups are successfully synthesized via direct polyacylation of sulfonated/quaternized monomers based on 2,2′‐dihydroxy‐1,1′‐binaphthyl (DHBN). Both proton exchange membranes (PEMs) and anion exchange membranes (AEMs) of the corresponding polyelectrolytes exhibit outstanding properties. Proton conductivity (116 mS cm^?1 at 30 °C) higher than Nafion 115 for the PEMs and OH^– conductivity (28.5–53.7 mS cm^?1 at 30 °C) comparable to Tokuyama A901 for the AEMs are accomplished. In addition, the AEMs can withstand 60 days’ aging in 1 mol L^?1 NaOH at 60 °C without degradation, as proved by ¹H NMR. More intriguingly, when starting from optically active (S)‐DHBN instead of racemic DHBN, an enhancement in proton conductivity of PEMs is observed for the first time, which opens a new door to optically active ion exchange membranes.     

甲醇直接氧化制备二甲氧基甲烷催化剂研究进展

作为一种新型的高性能柴油添加剂,二甲氧基甲烷的研究与生产受到越来越多的关注。论述了气相法甲醇部分氧化直接制备二甲氧基甲烷的机理,通过对甲醇部分氧化直接制备二甲氧基甲烷反应所用的Re、Ru、Mo、V等不同系列的催化剂的研究进展的综述,比较了各催化体系的特点;介绍了液相法甲醇直接氧化制二甲氧基甲烷的研究进展。最后对甲醇直接氧化制备二甲氧基甲烷提出了建议。     

Deactivation of VMgO x Catalysts by Coke in the Process of Isobutane Dehydrogenation with Carbon Dioxide

The process of isobutane dehydrogenation in the presence or absence of carbon dioxide was carried out over VMgO _x catalysts with different vanadium loading. The performed tests show that both the reaction atmosphere and physicochemical properties of the catalysts (related to vanadium content) have a great influence on the activity decrease and the carbonaceous deposit formation. Despite small ability of carbon dioxide to remove coke in the Boudouard reaction, the amounts of carbonaceous species deposited on the catalysts after the isobutane dehydrogenation under CO₂ atmosphere were even twice greater in comparison to those deposited in helium stream. Moreover, the rate of coke deposition during the dehydrogenation in the inert gas flow was only slightly dependent on the reaction time, in contrast to the process in carbon dioxide atmosphere. The results show that the coke formation on VMgO _x is enhanced predominantly by surface acidity of the catalysts, which grows with the vanadium content and the presence of CO₂ in the feed.     

Stability Enhancement of Pd Catalysts by Compositing with Polypyrrole Layer for Polymer Electrolyte Fuel Cell Electrodes

Pd catalyst composited with a conducting polymer of polypyrrole is prepared and investigated as a stable H₂ electrooxidation catalyst in an acidic condition. A significant stability enhancement of Pd by compositing electropolymerized polypyrrole can be observed and its mechanistic scheme for the stability is discussed through several electrochemical and physicochemical characterizations on the polypyrrole-composited Pd catalysts.     

Supported Pd and PdAu Nanoparticles on Ti-MCM-41 Prepared by a Photo-assisted Deposition Method as Efficient Catalysts for Direct Synthesis of H2O2 from H2 and O2

An efficient methodology to synthesize highly active Pd nanoparticles using a single-site photocatalyst under UV-light irradiation has been developed for the synthesis of hydrogen peroxide (H₂O₂) from H₂ and O₂. By the photo-assisted deposition (PAD) method, Pd precursor can be deposited directly on the photo-excited tetrahedrally coordinated metal-oxide moiety within the silica frameworks, and subsequently transformed into Pd nanoparticles by H₂ reduction. The mean diameter of the deposited Pd particles determined by CO adsorption and the catalytic activities in the direct synthesis of H₂O₂ were strongly dependent on the preparation method and kind and/or amount of metal-oxide moieties. Here, the use of Ti-containing mesoporous silica (Ti/Si = 0.01) acted as a most efficient support for the above reaction. The PAD method also provides PdAu bimetallic nanoparticles from an aqueous solution of mixture of PdCl₂ and HAuCl₄. The PdAu/Ti-MCM-41 catalyst prepared by the PAD method was shown to perform significantly better activity than the pure Pd/Ti-MCM-41.