Ceramic membranes modified with catalytic oxide films as ensembles of catalytic nanoreactors

Hybrid catalytic membrane systems have been produced by modifying porous ceramic membranes with metal oxide films. A two-layer cermet membrane consisting of a flexible stainless steel layer and an overlying porous TiO₂ ceramic layer and a ceramic titanium carbide membrane are examined. The membrane surfaces have been modified by the alkoxide method using colloidal organic solutions of metal complex precursors. Producing a tetragonal single-phase ZrO₂/Y₂O₃ coating on the cermet surface increases the abrasion strength of the ceramic layer. CO oxidation and the oxidative conversion of methane into synthesis gas and light hydrocarbons can be markedly intensified by modifying the membrane channels with Cu_0.03Ti_0.97O_2±δ and La + Ce/MgO catalysts, respectively. A method has been developed for depositing, onto the geometrical surface of a membrane, a film of the new single-phase oxide P_0.03Ti_0.97O_2±δ with an anatase structure and uniform pores of mean diameter 〈d〉 ～ 2 nm. Blocks of zeolite-like silicalite can be formed on the surface of the phosphorus-titanium oxide film. The resulting hybrid membrane is characterized by an anisotropic permeability depending on the flow direction. This property has an effect on conversion and selectivity in the nonoxidative dehydrogenation of methanol.     

Polyurethane‐mesoporous silica gas separation membranes

The concept of mixed matrix membrane comprising dispersed inorganic fillers into a polymer media has revealed appealing to tune the gas separation performance. In this work, the membranes were prepared by incorporation of mesoporous silica into polyurethane (PU). Mesoporous silica particles with different pore size and structures, MCM‐41, cubic MCM‐48 and SBA‐16, were synthesized by templating method and functionalized with 3‐aminopropyltriethoxysilane (APTES). High porosity and aminated surface of the mesoporous silica enhance the adhesion of the particles to the PU matrix. The SEM and FTIR results showed strong interactions between the particles and the PU chains. Moreover, the thermal stability of the hybrid PUs improved compared to the pure polymer. Gas transport properties of the membranes were measured for pure CO₂, CH₄, O₂, and N₂ gases at 10 bar and 25°C. The results showed that the gas permeabilities enhanced with increasing in the loading of modified mesoporous silica particles. High porosity and amine‐functionalized particles render opportunities to enhance the gas diffusivity and solubility through the membranes. The enhanced gas transport properties of the mixed matrix membranes reveal the advantages of mesoporous silica to improve the gas permeability (CO₂ permeability up to ~70) without scarifying the gas selectivity (α(CO₂/N₂)~ 30 for 5 wt% SBA‐16 content).     

An advanced gas/vapor permeation system for barrier materials: Design and applications to poly(ethylene terephthalate)

A new gas/vapor mixture permeation system is described to investigate the effect of organic molecules on oxygen (O₂) and carbon dioxide (CO₂) transport in barrier materials. Methanol vapor was considered as a flavor simulant mainly because of its conveniently high diffusion coefficient, which makes the experimental time accessible. A highly accurate syringe pump was used to introduce a desired activity level of vapor into gas feed stream. Adsorption of methanol on high energy surfaces is carefully characterized to prevent underestimation of methanol permeability. A special permeation cell was also developed to study the effect of interacting vapors on O₂ and CO₂ transport in barrier materials. Systematic permeation measurements were conducted for binary and ternary gas/vapor permeation measurements (e.g., MeOH/O₂ and O₂/CO₂/MeOH) to verify the feasibility of our new vapor/gas permeation system. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Gas permeation of porous organic/inorganic hybrid membranes

Selective gas permeation of porous organic/inorganic hybrid membranes via sol-gel route and its thermal stability are described. Separation performance of the hybrid membrane was improved compared with porous membranes governed by the Knudsen flow, and gas permeability was still much higher than that through nonporous membranes. Additionally, it was shown that these membranes were applicable at higher temperatures than organic membranes.SEM observation demonstrated that the thin membrane was crack-free. Nitrogen physisorption isotherms showed the pore size was in the range of nanometers. Gas permeability through this membrane including phenyl group was in the range of 10^–8 [cc(STP) cm/(cm² s cmHg)] at 25°C. The ratios of O₂/N₂ and CO₂/N₂ were 1.5 and 6.0, respectively, showing the permeation was not governed by the Knudsen flow. The permeability decreased as the temperature increased. Furthermore, the specific affinity between gas molecules and surface was observed not only in the permeation data of the hybrid membranes but in the physisorption data. These results suggested that the gas permeation through the hybrid membrane was governed by the surface flow mechanism.Thermal analysis indicated that these functional groups were still stable at higher temperatures. The phenyl group especially remained undamaged even at 400°C.     

Calcium peroxosilicates

Calcium peroxosilicates CaO·nSiO₂·xH₂O·yH₂O₂ (n = 1, 2) were synthesized by three methods: (1) the reaction of CaSiO₃·nH₂O (～7% CaSiO₃ suspension in water) with 50.7, 73.4, and 92% H₂O₂ at 0–5°C produced compositions CaSiO₃·6H₂O·2H₂O₂, CaSiO₃·2H₂O·4H₂O₂, and CaSiO₃·3H₂O·8H₂O₂, respectively; (2) the reaction of CaSiO₃·17H₂O with 50.7 and 73.4% H₂O₂ at 0–5°C produced the solvate CaO·2SiO₂·4H₂O·0.15H₂O₂; and (3) the reaction of CaSiO₃·3H₂O with H₂O₂ vapor at 5°C in the absence of anhydrone produced the solvate CaSiO₃·3.5H₂O·0.5H₂O₂. The products were characterized by X-ray powder diffraction, thermogravimetry, and IR spectroscopy.     

Effect of top layer swelling on the oxygen/nitrogen separation by surface modified polyurethane membranes

Cobalt(II) was chelated on the surface of a hydroxyl terminated polybutadiene (HTPB) based polyurethane (PU) membrane. The surface of a HTPB based PU membrane was first modified by ethylenediamine (EA) plasma. The cobalt chelated membrane was prepared by immersing the plasma treated membrane into a cobalt(II)/formamide solution for various length of time. For a fair comparison, the untreated and plasma treated membranes were also immersed in formamide solution. The gas transport properties of all three membranes were compared. Without solvent immersion, the O₂/N₂ selectivity increased from 2.6 to 3.1 after EA plasma treatment. But the permeability decreased from 0.88 GPU to 0.35 GPU. The selectivity was further improved to 4.4 by immersing the plasma treated membrane in a solution of CoCl₂·6H₂O/formamide for 1 h, but the permeability decreased to 0.23 GPU. The solvent immersion had little effect on the transport properties of the untreated membrane. But the transport properties of the plasma treated and cobalt chelated membranes were greatly affected by the formamide immersion. The oxygen and nitrogen permeabilities of the modified top layers could be calculated from a series model for composite membranes. It was found that both the permeability and selectivity of the top layer of the plasma treated membrane increased with the solvent immersing time. For the top layer of the cobalt chelated membrane, the gas permeability first decreased after 1 h immersion and then increased after further immersion in CoCl₂·6H₂O/formamide solution. The selectivity of cobalt chelated membrane increased as the gas permeability decreased and vice versa. These results implied that the EA grafting enhanced the O₂/N₂ selectivity by increasing its oxygen affinity but the cobalt chelating increased the O₂/N₂ selectivity by enhancing the size sieving effect.     

The influence of pyrocarbon modification on the physicochemical characteristics of the surface of pores and transport properties of inorganic membranes

The structure of pyrocarbon crystallites deposited on the surface of the pore channels of TRUMEM composite inorganic membranes (TiO₂ on porous steel) was studied by X-ray diffraction, X-ray photoelectron spectroscopy, and scanning electron microscopy. According to the X-ray data, the lattice of pyrocarbon crystallites of size L _c=40.0 nm has hexagonal symmetry with d ₀₀₂=3.368 Å. The deposition of pyrocarbon crystallites with L _c up to 1.5 nm was identified by X-ray photoelectron spectroscopy and scanning electron microscopy. Coating the pore channels of membranes with pyrocarbon decreased the density of the electric charge on their surface by a factor of ～5.5. The temperature dependences of the hydrodynamic permeability coefficient were obtained for the initial and pyrocarbon-modified membranes when polar and nonpolar fluids flowed through them. The electrostatic force and energy of the interaction of ethanol molecules with each other and the surface of pores were calculated; the results were compared with the O-H···O H-bond energy. The main reason for the formation of alcohol adsorption layers was the formation of H-bonds between its molecules and O-H···O atoms on the surface of pores.     

Pore Modification in Porous Ceramic Membranes With Sol-Gel Process and Determination of Gas Permeability and Selectivity

Summary: The aim of the study was to investigate the variation in total surface area, porosity, pore size, Knudsen and surface diffusion coefficients, gas permeability and selectivity before and after the application of sol-gel process to porous ceramic membrane in order to determine the effect of pore modification. In this study, three different sol-gel process were applied to the ceramic support separately; one was the silica sol-gel process which was applied to increase porosity, others were silica-sol dip coating and silica-sol processing methods which were applied to decrease pore size. As a result of this, total surface area, pore size and porosity of ceramic support and membranes were determined by using BET instrument. In addition to this, Knudsen and surface diffusion coefficients were also calculated. After then, ceramic support and membranes were exposed to gas permeation experiments by using the CO₂ gas with different flow rates. Gas permeability and selectivity of those membranes were measured according to the data obtained. Thus, pore surface area, porosity, pore size and Knudsen diffusion coefficient of membrane treated with silica sol-gel process increased while total surface area was decreasing. Therefore, permeability of ceramic support and membrane treated with silica sol-gel process increased, and selectivity decreased with increasing the gas flow rate. Also, surface area, porosity, pore size, permeability, selectivity, Knudsen and surface diffusion coefficients of membranes treated with silica-sol dip coating and silica-sol processing methods were determined. As a result of this, porosity, pore size, Knudsen and surface diffusion coefficients decreased, total surface area increased in both methods. However, viscous flow and Knudsen flow permeability were detected as a consequence of gas permeability test and Knudsen flow was found to be a dominant transport mechanism in addition to surface diffusive flow owing to the small pore diameter in both methods. It was observed that silica-sol processing method had lower pore diameter and higher surface diffusion coefficient than silica-sol dip coating method.     

<Emphasis Type="Italic">O</Emphasis>-vinylacetoxime as a hydrogen bond acceptor

According to quantum chemical calculations (B3LYP/6-311G*) and IR spectroscopy the basicity of oxygen atom of O-vinylacetoxime is substantially lower than that of O-ethylacetoxime and is comparable to the basicity of phenyl vinyl and diphenyl ethers. In CCl₄ solution, O-vinylacetoxime gives H-complexes wit methanol by formation of N···HO bonds. With phenol and trifluoroacetic acid under these conditions it enters in the reaction of electrophilic addition. O-Ethylacetoxime in inert media forms with methanol and phenol two types of H-complexes with the N···HO or O···HO bonds.     

Surface reactions of dimethyl ether on γ-Al2O3

The surface reactions of dimethyl ether (DME) on industrial alumina (γ-Al₂O₃) were studied by chromatographic analysis of the products at the outlet of the flow reactor and (independently) by diffuse reflectance IR spectroscopy. The major products of the reactions at 250°С were found to be methanol formed in the reaction of DME with hydroxyl groups (the 3720 and 3674 cm^–1 bands in the diffuse reflectance spectrum) and various methoxy groups (the 1121, 1070, 695, and 670 cm^–1 bands in the differential spectra). The presence of molecularly adsorbed methanol was confirmed by experiments with methanol fed in a high-temperature IR cell. The interaction of the resulting methanol molecule with the hydroxyl group led to the formation of a water molecule in the gas phase and a methoxy group on the oxide surface. Strong adsorption of molecular DME was revealed, which was favored by an increase in the temperature of the preliminary calcination of oxide from 250 to 450–500°С; treatment of alumina with water vapor after its preliminary contact with DME led to a recovery of the hydroxyl coating and a replacement of molecularly adsorbed DME with hydroxyl. The thermal effect recorded in a flow reactor was positive during the adsorption of DME and negative during the desorption of weakly bonded DME. Schemes of formation of methoxy groups in the interaction of DME and methanol with surface hydroxyls were suggested.     

T型及KA分子筛膜的制备、修复及其天然气脱水蒸气性能研究

天然气在长距离输送之前必须进行脱水蒸气,膜分离法是天然气脱水蒸气的有效方法,其中膜材料是关键,而分子筛膜因具有均一的孔径、规则的孔道、良好的稳定性而备受关注。本研究选择孔径为3-5 μm,直径为2 cm的圆片状多孔氧化铝陶瓷作为成膜基底,通过在基底上预涂晶种后原位生长得到了T型和NaA分子筛膜,NaA分子筛膜进一步经过金属离子交换获得了KA分子筛膜,最后将两种分子筛膜应用于水蒸气含量为3.5%的甲烷气体(作为模型天然气)进行天然气脱水蒸气实验。研究结果表明,T型及KA分子筛膜对模型天然气脱水蒸气的H₂O/CH₄选择性分别为2.80和3.16。进而采用表面涂层法对分子筛膜中的缺陷进行了修复,从而有效提高了其模型天然气脱水蒸气性能,修复后的T型及KA分子筛膜的H₂O/CH₄选择性分别达到了10.52和17.71,水蒸气的渗透系数分别为104397 Barrer和28200 Barrer,甲烷损失率分别仅为2%和1%,修复后的两种分子筛膜皆具有良好的稳定性。     

A Ga2O·11Al2O3 nanonet prepared by interfacial reaction growth approach and its application in fabricating GaN nanowires

A Ga₂O·11Al₂O₃ nanonet was synthesized by using Ga₂O₃ powder as the precursor to generate Ga₂O vapor in H₂ atmosphere which further reacted with Al₂O₃ at 730 °C to form Ga₂O·11Al₂O₃ at the interfaces of a porous anodic aluminum oxide (AAO) template. The prepared Ga₂O·11Al₂O₃ nanonet then served as a Ga₂O-stablizing reservoir to fabricate single crystal GaN nanowires. The residual Ga₂O₃ powder at the surface of the produced Ga₂O·11Al₂O₃ nanonet and the metallic Ga or Ga₂O from the Ga₂O·11Al₂O₃ decomposition reacted with ammonia to yield GaN nanowires at 780 °C. The reaction mechanisms were investigated.     

Separation of nitrogen and oxygen gases by polymeric membrane embedded with magnetic nano‐particle

Asymmetric polyethersulfone (PES) micro‐porous flat sheet membranes were prepared by the phase inversion method (PIM) and used as the support. PES‐PDMS composite membranes were fabricated with coating polydimethylsiloxane on the surface of PES membrane. The FluidMAG‐PAD was coated on PES and PES‐PDMS membrane to prepare super‐paramagnetic membranes for separation of oxygen from nitrogen. Permeance and O₂/N₂ selectivity were evaluated in the absence or presence of external magnetic field. In the absence of external magnetic field, the super‐paramagnetic polymer provides larger surface area leading to extended sites for oxygen adsorption. In the presence of magnetic field, the super‐paramagnetic particles obtained magnetic property leading to a pronounced interaction with oxygen resulting in elevated selectivity and permeability. Copyright © 2011 John Wiley & Sons, Ltd.     

Synthesis,crystal structure,and thermal behavior of dimethylgold(III) acetate

A dimethylgold(III) compound with an acetate fragment [(CH₃)₂AuOCOCH₃]₂ has been synthesized. The complex was identified from the melting point, IR, ¹H NMR, and mass spectrometry data. The temperature dependence of saturated vapor pressure over crystals has been measured and the thermodynamic parameters of sublimation have been determined by Knudsen’s effusion method with mass spectrometric measurements of the composition of the gas phase: ΔH _subl = 100.87 kJ·mol^?1, ΔS _subl = 216.67 J·mol^?1·K^?1. The thermal behavior of the solid compound was investigated by differential thermal analysis. The compound was studied by X-ray diffraction. Crystal data for C₈H₁₈Au₂O₄: a = 12.214(5) Å, b = 14.307(3) Å, c = 7.6635(15) Å; β = 103.39(3)°, Z = 4, d _calc = 2.917 g/cm³, space group P2(1)/c, R = 0.0261. The [(CH₃)₂AuOCOCH₃]₂ dimer complex with an Au...Au distance of 2.989 Å is the structural unit. The gold atom has a square plane environment of two carbon and two oxygen atoms; the Au-O distances vary from 2.118 Å to 2.139 Å. The molecules are arranged in chains linked by van der Waals interactions.     

NaA Zeolite Membrane with High Performance Synthesized by Vapor Phase Transformation Method

IntroductionZeolitemembranes ,asaremarkablebranchofinor ganicmembrane ,havepotentialadvantagesinmanyappli cationssuchascatalysisandseparation ,chemicalsensors ,ascousticwavedevices ,andmicroelectronicdevicesduetotheiruniformporesizeatthemolecularlevelandresis tancetohightemperature .1 5For 10years ,manyre searchershavepaidconsiderableattentiontosynthesisofzeolitemembraneswithhighperformance .Amongthere portedzeolitemembranes ,mostattentionwasfocusedonsynthesisofMFI typezeolitemembranebecausei…     

Preparation and characterization of H<Subscript>3</Subscript>PW<Subscript>12</Subscript>O<Subscript>40</Subscript>/ZrO<Subscript>2</Subscript> catalyst for carbonation of methanol into dimethyl carbonate

A H₃PW₁₂O₄₀/ZrO₂ catalyst for effective dimethyl carbonate (DMC) formation via methanol carbonation was prepared using the sol–gel method. X-ray photoelectron spectra showed that reactive and dominant (63%) W(VI) species, in WO₃ or H₂WO₄, enhanced the catalytic performances of the supported ZrO₂. The mesoporous structure of H₃PW₁₂O₄₀/ZrO₂ was identified by nitrogen adsorption–desorption isotherms. In particular, partial sintering of catalyst particles in the duration of methanol carbonation caused a decrease in the Brunauer–Emmett–Teller surface area of the catalyst from 39 to 19 m²/g. The strong acidity of H₃PW₁₂O₄₀/ZrO₂ was confirmed by the desorption peak observed at 415 °C in NH₃ temperature-programmed desorption curve. At various reaction temperatures (T?=?110, 170, and 220 °C) and CO₂/N₂ volumetric flow rate ratios (CO₂/N₂?=?1/4, 1/7, and 1/9), the calculated catalytic performances showed that the optimal methanol conversion, DMC selectivity, and DMC yield were 4.45, 89.93, and 4.00%, respectively, when T?=?170 °C and CO₂/N₂?=?1/7. Furthermore, linear regression of the pseudo-first-order model and Arrhenius equation deduced the optimal rate constant (4.24?×?10^?3 min^?1) and activation energy (E_a?=?15.54 kJ/mol) at 170 °C with CO₂/N₂?=?1/7 which were favorable for DMC formation.     

Humidity controlled thermal analysis

The low temperature formation of crystalline zinc oxide via thermal decomposition of zinc acetylacetonate monohydrate C₁₀H₁₄O₄Zn·H₂O was studied by humidity controlled thermal analysis. The thermal decomposition was investigated by sample-controlled thermogravimetry (SCTG), thermogravimety combined with evolved gas analysis by mass spectrometry (TG-MS) and simultaneous differential scanning calorimetry and X-ray diffractometry (XRD-DSC). Decomposition of C₁₀H₁₄O₄Zn·H₂O in dry gas by linear heating began with dehydration around 60°C, followed by sublimation and decomposition above 100°C. SCTG was useful because the high-temperature parallel decompositions were inhibited. The decomposition changed with water vapor in the atmosphere. Formation of ZnO was promoted by increasing water vapor and could be synthesized at temperatures below 100°C. XRD-DSC equipped with a humidity generator revealed that C₁₀H₁₄O₄Zn·H₂O decomposed directly to the crystalline ZnO by reacting with water vapor.     

Separation performance of foils from Pd—In(6%)—Ru(0.5%), Pd—Ru(6%), and Pd—Ru(10%) alloys and influence of CO<Subscript>2</Subscript>, CH<Subscript>4</Subscript>, and water vapor on the H<Subscript>2</Subscript> flow rate through the test membranes

The H₂ flow rate through the 30-μm thick foil from Pd—Ru(6%) and Pd—Ru(10%) alloys at 673 and 773 K was found to be controlled by the diffusion of H atoms in the foil bulk. The interrelation between hydrogen permeability through the Pd—In(6%)—Ru(0.5%), Pd—Ru(10%), Pd—Ru(6%), and Pd—Ag(23%) membranes and the permeability pre-exponential factors in the Sieverts equation in the 573—773 K temperature interval indicated that the hydrogen permeability depended on the structural characteristics of palladium alloys. The influence of the CO₂, CH₄, and water vapor impurities on the H₂ flow rate through the studied membranes depended on the driving force nature (the sweep gas or transmembrane pressure) used for the development of the partial hydrogen pressure difference across the membrane. The negative influence of CH₄ and CO₂ was observed only when using a transmembrane pressure and at the impurity content of 20% or more. This effect increased with increasing temperature in the 573—773 K range, with the influence of CO₂ being more pronounced due to its reaction with hydrogen leading to the formation of CO. The influence of water vapor was studied at its 11—23% content in hydrogen and at 573 and 773 K of temperature. The negative influence of water vapor was found to subside as its content in the hydrogen mixture decreased and the temperature increased. It was shown that water vapor can be used as a sweep gas and at T = 773 K its influence on the H₂ flow rate through the membrane was almost the same as that of N₂.     

多孔材料负载金催化剂的制备与应用*

本文综述了微孔材料和介孔材料负载型金催化剂的制备、表征与应用研究的最新进展,从多孔载体的选择（氧化物、微孔分子筛、介孔氧化物、介孔分子筛和介孔碳材料）、金的最新负载方法（沉积-沉淀法、溶胶-凝胶法、原位法/一步法和化学气相沉积法）与表征及其催化性能（一氧化碳低温氧化、氢气/氧气直接合成过氧化氢、直接合成环氧丙烷和有机物的选择性氧化）等方面详尽地评述了微孔材料和介孔材料负载型金催化剂研究概况。同时,提出了多孔材料负载金催化剂存在的一些问题,并展望了其研究和发展的方向。     

Separation of alcohols and alcohols/O2 mixtures using zeolite MFI membranes

Two different types of supported silicalite membranes were employed for the separation of alcohols and alcohols/O₂ mixtures: in one of them the zeolite material was deposited on the top of the γ-alumina supports, while in the other the zeolitic material was mainly present in the porous structure of the α-alumina supports. While both kinds of membranes were able to separate the above mixtures, the second type of membranes having the zeolite material inside the support performed more efficiently. The maximum selectivity reported in this work is 7415 for the ethanol/O₂ separation in an ethanol/methanol/O₂ mixture. For a better understanding of the separation mechanism, the performance of both zeolite membranes was compared to that of a mesoporous silica membrane. Also, the adsorption of methanol and propanol on silicalite crystals was measured using a microbalance.