含氨基聚芳醚酮/磺化聚芳醚酮砜中高温质子交换复合膜的制备与性能研究

以自制的高磺化度磺化聚芳醚酮砜(SPAEKS)和含有氨基的聚芳醚酮(Am-PAEK)为原料,通过共溶剂涂膜法制备了不同重量比例的Am-PAEK/SPAEKS复合膜.通过高温(160℃)处理使氨基和磺酸基团在复合膜内形成交联,制得交联型复合膜.复合膜的热性能、尺寸稳定性、阻醇性能有所提高,而且交联型复合膜中的Am-PAEK/SPAEKS-C-3质子传导率在120℃时达到了0.0892 S/cm,高于在相同测试条件下SPAEKS膜的0.0654 S/cm和Nafion膜的0.062 S/cm,而其甲醇渗透系数在25℃时达到0.14×10-6cm2/s,低于SPAEKS膜的0.85×10-6cm2/s和Nafion膜的2×10-6cm2/s.实验结果表明,Am-PAEK/SPAEKS交联型复合膜有望在中高温质子交换膜燃料电池中得到应用.     

An ultrathin self-humidifying membrane for PEM fuel cell application: fabrication, characterization, and experimental analysis

An ultrathin poly(tetrafluoroethylene) (PTFE)-reinforced multilayer self-humidifying composite membrane (20 microm, thick) is developed. The membrane is composed of Nafion-impregnated porous PTFE composite as the central layer, and SiO2 supported nanosized Pt particles (Pt-SiO2) imbedded into the Nafion as the two side layers. The proton exchange membrane (PEM) fuel cell employing the self-humidifying membrane (Pt-SiO2/NP) turns out a peak power density of 1.40 W cm(-2) and an open circuit voltage (OCV) of 1.032 V under dry H2/O2 condition. The excellent performance is attributed to the combined result of both the accelerated water back-diffusion in the thin membrane and the adsorbing/releasing water properties of the Pt-SiO2 catalyst in the side layers. Moreover, the inclusion of the hygroscopic Pt-SiO2 catalyst inside the membrane results in an enhanced anode self-humidification capability and also the decreased cathode polarization (accordingly an improved cell OCV). Several techniques, such as transmission electronic microscopy, scanning electronic microscopy, energy dispersive spectroscopy, thermal analysis and electrochemical impedance spectroscopy etc., are employed to characterize the Pt-SiO2/NP membrane. The results are discussed in comparison with the plain Nafion/PTFE membrane (NP). It is established that the reverse net water drag (from the cathode to the anode) across the Pt-SiO2/NP membrane reaches 0.16 H2O/H+. This implies a good hydration of the Pt-SiO2/NP membrane and thus ensures an excellent PEM fuel cell performance under self-humidification operation.     

Simple fabrication of Cu~(2+) doped calcium alginate hydrogel filtration membrane with excellent anti-fouling and antibacterial properties

Herein,copper ion doped calcium alginate(Cu~(2+)/CaAlg) composite hydrogel filtration membranes were prepared by using natural polymer sodium alginate(NaAlg) as raw material.The thermal stability and structure of the composite membranes were characterized by thermogravimetric analysis and infrared spectroscopy.The mechanical strength,anti-fouling performance,hydrophilicity and filtration performance of the membrane were studied.The results show that Cu~(2+)/CaAlg hydrogel membrane has excelle nt mechanical properties and thermal stability.The anti-swelling ability of the membrane was greatly enhanced by doping Cu~(2+).After three alternate filtration cycles,the flux recovery rate of Cu~(2+)/CaAlg hydrogel membrane can still reach 85%,indicating that the membrane has good antipollution performance.When the operation pressure was 0.1 MPa,the rejection of coomassie brilliant blue G250 reached 99.8% with a flux of 46.3 L m ~2 h ~1,while the Na_2 SO_4 rejection was less than 10.0%.The Cu~(2+)/CaAlg membrane was recycled after 24 h in the filtration process,and its flux and rejection rate did not decrease significantly,indicating that the hydrogel membrane has long-term application potential.The Cu~(2+)/CaAlg membrane has a wide range of applications prospect in dye desalination,fine separation and biopharmaceutical technology fields.     

Effect of emulsifier type on droplet disruption in repeated shirasu porous glass membrane homogenization

The influence of various emulsifier types (anionic, nonionic, and zwitterionic) on the mean particle size, transmembrane flux, and membrane fouling in repeated membrane homogenization using a Shirasu porous glass (SPG) membrane has been investigated. Oil-in-water (O/W) emulsions (40 wt % corn oil stabilized by 0.06-2 wt % sodium dodecyl sulfate (SDS) or 0.1-2 wt % Tween 20 at pH 3 or 0.5-2 wt % beta-lactoglobulin (beta-Lg) at pH 7) were prepared by passing coarsely emulsified feed mixtures five times through the membrane with a mean pore size of 8.0 microm under the transmembrane pressure of 100 kPa. The flux increased as the number of passes increased, tending to a maximum limiting value. The maximum flux for the Tween 20-stabilized emulsions (5-47 m3.m(-2).h(-1)) was smaller than that for the SDS-stabilized emulsions (29-60 m3.m(-2).h(-1)) because less energy was needed for the disruption of a SDS-stabilized droplet due to the lower interfacial tension. The mean particle size after five passes was 4.1-6.8 and 6.4-8.7 mum for 0.1-2 wt % SDS and Tween 20, respectively. The flux in the presence of beta-Lg was much smaller than that in the presence of SDS and Tween 20, which was a consequence of more pronounced membrane fouling, due to the protein adsorption to the membrane surface. After five passes through the membrane, the fouling resistance in the presence of 2 wt % beta-Lg (1.1 x 10(10) 1/m) was 2 orders of magnitude higher than that for 0.5 wt % Tween 20 and an order of magnitude higher than the membrane resistance. If a clean membrane was used in the fifth pass, a 2-fold reduction of the fouling resistance was observed.     

Selective permeation of CO2 through poly 2-(N,N-dimethyl)aminoethyl methacrylate membrane prepared by plasma-graft polymerization technique

A membrane having an amine moiety was prepared by plasma-grafting 2-(N,N-dimethyl)aminoethyl methacrylate (DAMA) onto a microporous polyethylene substrate. Permselectivity of the membrane for CO₂ over N₂ was achieved in both dry and water swollen conditions. When the CO₂ partial pressure in the feed gas was 0.047 atm, the selectivity of CO₂ over N₂ reached 130 for the highly swollen water containing membrane. This value was found to agree with that obtained with a mobile carrier membrane (supported liquid membrane) using DAMA as the carrier. The effects of several experimental conditions such as degree of grafting, feed partial pressure and temperature on the membrane performance were studied. It was suggested that the membrane acted as a fixed carrier membrane for CO₂ facilitated transport in under the dry condition and acted as a fixed reaction site membrane in the water swollen condition. The carrier transport mechanism is discussed for dry and aqueous membranes.     

TMSP—PMDSP共聚物膜的氧,氮透过性

研究了三甲基硅丙炔(TMSP) 和五甲基二硅丙炔(PMDSP) 的共聚物膜对O_2、N_2气体的透过行为。发现 TMSP-PMDSP共聚物膜对O_2、N_2气体的透过活化能为负值,透过系数随温度升高而下降;受热历程不同,气体在膜中的透过行为也不相同。膜两侧气体压差不同时,气体在膜中的透过系数亦发生变化。用氟化物HFBM对共聚物膜表面进行了化学改性,改性膜的P_(O_2)/PN_2值达到3.52。     

磺化双酚芴型聚醚醚酮质子交换膜的制备及其在钒流电池中的应用

以双酚芴为结构单元合成双酚型聚醚醚酮聚合物,聚醚醚酮经浓硫酸磺化在双酚芴结构单元中引入磺化基团制备出聚醚醚酮质子交换膜(SF-PEEK)。 用傅里叶变换红外光谱(FTIR)、核磁共振氢谱(¹H NMR)、热重分析(TG)、原子力显微镜(AFM)和扫描电子显微镜(SEM)等方法对聚醚醚酮质子交换膜的结构进行表征。 结果表明,磺酸基团被成功地在聚醚醚酮侧基上,SF-PEEK膜具有明显的亲水疏水微相分离形貌,磺酸基团相互聚集成形成离子通道。 SF-PEEK膜离子交换容量(IEC)达到1.97 mmol/g时,其电导率达到4.15×10^-2 S/cm,略低于Nafion117膜的5.67×10^-2 S/cm,但其钒离子渗透率仅为Nafion117膜的20.1%,表现出极好的离子选择性。 在钒流电池测试中,SF-PEEK膜在不同电流密度下库伦效率均高于Nafion117膜,其中IEC为1.97 mmol/g的SF80-PEEK608(80为SF的物质的量分数,608为60 ℃反应8 h)库伦效率在电流密度为40 mA/cm²时达到最大值80.9%,高于Nafion117膜的78.8%。 在自放电测试中,以SF80-PEEK608膜组装的电池的自放电时间为90 h,高于Nafion117膜的57 h。     

NafionTM膜表面改性用等离子体聚合方法提高膜的阳离子选择性

采用辉光放电等离子体聚合方法 ,以 C2 H4 和 NH3 为单体 ,在 Nafion TM膜表面沉积一层含氨基及酰氨基的类聚乙烯阴离子交换膜 ,提高了 Nafion TM膜对阳离子的选择性 ,同时不显著增加膜电阻 .由 SEM确定该等离子体聚合膜厚约 0 .5μm,用红外光谱及 X光电子能谱表征膜结构 .采用四电极法测量膜电阻 ,膜对质子的选择性由 Cu2 + 的迁移数 t Cu表征 ,用二室隔膜装置 (0 .2 5mol/L Cu Cl2 -0 .5mol/L HCl|等离子体处理膜 |1 mol/L HCl)测量 t Cu. O2 等离子体预处理 Nafion TM膜有利于沉积膜在 Nafion TM膜上的沉积并与 Nafion TM膜紧密结合 .经改性后的 Nafion TM膜电阻值仍然很小 ,在 1 mol/L HCl溶液中电阻小于 0 .5Ω· cm2     

A STUDY ON MEMBRANE PROCESS WITH |?-ALUMINA MEMBRANE REACTOR FOR ETHYLBENZENE DEHYDROGENATION TO STYRENE

The membrane reaction of ethylbenzene(EB) dehydrogenation to styrene(ST) has been studied by using K2O/Fe2O3 industrial catalyst and alumina ceramic membrane developed by our institute. In comparison with the packed bed reactor (that is, plug flow reactor, abbr. PFR) in industrial practice, the yield of styrene was increased by 5%~10% in the membrane reactor. Furthermore, mathematical modeling of membrane reaction has been studied to display the principle of optimal match between the catalytic activity and the membrane permeability.     

SIFSIX-3-Ni膜的制备及氢气分离性质

利用(NH₄)₂SiF₆修饰大孔玻璃基底后, 在溶剂热条件下制备了SIFSIX-3-Ni膜, 并研究了温度和浓度对制备SIFSIX-3-Ni膜的影响. 能谱分析(XPS)结果表明大孔玻璃表面引入了氟元素. SIFSIX-3-Ni膜的粉末X射线衍射(PXRD)峰位置和模拟结果一致, 表明成功制备出SIFSIX-3-Ni膜. 从扫描电子显微镜(SEM)照片中观察到膜连续均匀, 厚度约为20 μm. 热重分析(TGA)结果表明, 活化前的膜没有客体分子. 单组分测试结果表明, 膜的H₂, CO₂和N₂渗透量分别为6.83×10 ^-6, 7.42×10 ^-7和8.89×10 ^-7 mol·m ^-2·s ^-1·Pa ^-1, H₂/CO₂和H₂/N₂的理想分离比分别为9.20和7.68. 在连续测试5 h后, H₂, CO₂和N₂渗透量基本保持不变, 表明SIFSIX-3-Ni膜具有很好的稳定性.     

Simulation study on the catalytic decomposition of hydrogen iodide in a membrane reactor with a silica membrane for the thermochemical water-splitting IS process

Catalytic decomposition of hydrogen iodide in a membrane reactor was investigated theoretically for the application to the hydrogen production step in the thermochemical iodine–sulfur (IS) process. Characteristics of the membrane reactor were evaluated using observed permeances of H₂ and HI in a homemade silica membrane that was prepared by chemical vapor deposition (CVD) method (selectivity of H₂/HI: 650). The effect of the H₂/I₂ selectivity on the performance of the membrane reactor was evaluated by simulation since I₂ permeance through the homemade silica membrane could not be determined so far because of the difficulty of the measurements. It was found from the simulation study that the conversion of over 0.9 would be attainable using the membrane reactor with the homemade silica membrane. Design criterion of the membrane reactor was discussed using the relationships between the ratio of reaction zone volume to the membrane surface area, the dimensionless reactor length and the conversion.     

Nafion/TiO<Subscript>2</Subscript> hybrid membrane fabricated via hydrothermal method for vanadium redox battery

To improve the performance of Nafion membrane as a separator in vanadium redox battery (VRB) system, a Nafion/TiO₂ hybrid membrane was fabricated by a hydrothermal method. The primary properties of this hybrid membrane were measured and compared with the Nafion membrane. The Nafion/TiO₂ hybrid membrane has a dramatic reduction in crossover of vanadium ions compared with the Nafion membrane. The results of scanning electron microscope, energy dispersive X-ray spectroscopy, and X-ray diffraction of the hybrid membrane revealed that the TiO₂ phase was formed in the bulk of the prepared membrane. Cell tests identified that the VRB with the Nafion/TiO₂ hybrid membrane presented a higher coulombic efficiency (CE) and energy efficiency (EE), and a lower self-discharge rate compared with that of the Nafion system. The CE and EE of the VRB with the hybrid membrane were 88.8% and 71.5% at 60 mA cm⁻², respectively, while those of the VRB with Nafion membrane were 86.3% and 69.7% at the same current density. Furthermore, cycling tests indicated that the Nafion/TiO₂ hybrid membrane can be applied in VRB system.     

SUPPRESSION OF CELL ADHESION ON POLYACRYLONITRILE-BASED MEMBRANES BY THE ANCHORING OF PHOSPHOLIPID MOIETIES

In this work, the membrane surface of poly（acrylonitrile-co-2-hydroxyethyl methacrylate） （PANCHEMA） was chemically modified by anchoring of phospholipid moieties. The process involved the reaction of hydroxyl groups on the membrane surface with 2-chloro-2-oxo-1,3,2-dioxaphospholane （COP） followed by the ring-opening reaction of COP with trimethylamine. Chemical differences between the original and the modified membranes were characterized by FT-IR and XPS, It was found that the amount of macrophage adhered on the modified membrane surface is substantially lower than that on polyacrylonitrile （PAN） and PANCHEMA membranes under the same condition, The morphological change of the adherent cell is also suppressed by the generation ofphospholipid moieties on the membrane surface.     

Properties of oxygen permeation and partial oxidation of methane in La0.6Sr0.4CoO3−δ (LSC)–La0.7Sr0.3Ga0.6Fe0.4O3−δ (LSGF) membrane

The oxygen separation membrane having perovskite structure for the partial oxidation of methane to synthesis gas was prepared. La_0.7Sr_0.3Ga_0.6Fe_0.4O_3−δ (LSGF) perovskite membrane coated with La_0.6Sr_0.4CoO_3−δ (LSC) (M1), and the one side of M1 membrane coated with NiO (M2) was prepared to examine the partial oxidation of methane. The single oxygen permeations of the LSC + LSGF (M1) membrane and NiO coated membrane (M2) were measured. The oxygen permeation flux in M1 membrane was higher than that of M1 membrane at 850 °C.

The partial oxidation experiment of methane using the prepared membranes was examined at 850 °C. The value of CH₄ conversion and CO selectivity of M2 membrane was higher than that of M1 membrane.

NiO/NiAl₂O₄ catalyst was used to improve the methane conversion, and the partial oxidation experiment of methane with M1 membrane was examined at 850 °C. The CH₄ conversion was 88%, and CO selectivity was 100%.     

Formation of appropriate sites on nanofiltration membrane surface for binding TiO2 photo-catalyst: Performance, characterization and fouling-resistant capability

Titanium dioxide (TiO₂) nanoparticles were assembled on the surface of nanofiltration blend membrane. For settling TiO₂ on the membrane surface, two membrane categories were used: (i) unmodified polyethersulfone (PES)/polyimide (PI) blend membrane, and (ii) –OH functionalized PES/PI blend membrane with different concentrations of diethanolamine (DEA). These membranes were radiated by UV light after TiO₂ depositing with different concentrations. 15 min immersion in colloidal suspension and 15 min UV irradiation with 160 W lamps were used for modification. The modification resulted in the formation of a photo-catalytic property with enhanced membrane hydrophilicity. The self-assembly of TiO₂ nanoparticles was established through coordinance bonds with –OH functional groups on the membrane surface. A comparison between the UV irradiated TiO₂ deposited blend membrane and deposited-functionalized blend membranes showed that –OH groups originate excellent adhesion of TiO₂ nanoparticles on the membrane surface, increase reversible deposition, and diminish irreversible fouling. The membranes were characterized using SEM, FTIR, EDX, contact angle, cross flow filtration, and antifouling measurements. SEM images show that the presence of –OH groups on the DEA-modified membrane surface is the main parameter for extra uniformly settlement of TiO₂ nanoparticles on the membrane surface. This procedure is a superior technique for modification of PES/PI nanofiltration membranes to enhance water flux and minimization membrane fouling.     

在不锈钢网上快速制备连续致密 Silicalite-1分子筛膜

开发了一种在不锈钢网基底上快速制备连续致密Silicalite-1(Si-MFI)分子筛膜的新方法. 该制膜过程包括用含有聚氧乙烯(PEO)高分子的氧化硅溶液对不锈钢网基底进行预处理和在预处理后的基底上用二次生长法制备分子筛膜2个步骤. 通过该方法可在12 h内制备连续致密的不锈钢网支撑的Si-MFI分子筛膜. SEM分析结果表明, 所制备的Si-MFI分子筛膜连续且致密, 而XRD分析结果表明, 膜中的Si-MFI微晶具有高结晶度. 用膜渗透分离装置及气相色谱仪测试了Si-MFI膜的渗透性能及对CO₂和N₂的分离性能, 结果显示, 该Si-MFI膜具有很好的渗透性能, 并对CO₂和N₂具有很好的分离性能.     

采用Nafion粘结剂的PEMFC氧电极研究

研究了聚合物电解质燃料电池（PEMFC）中以Nation溶液取代PTFE乳液作粘结剂的效果．并对催化剂层内Nafion含量进行了优化，同时探讨了气体工作压力和离子交换膜的影响，实验发现：1．使用Nafion溶液后显著提高电池性能，Nafion含量为2mg·cm－2时性能技好；2．气体压力增大改善了电池位能；3．使用Nafion115膜的电池性能优于使用Nafion117膜的电池．要进一步提高电池性能，减小欧姆控制区的斜率是必要的．     

Synergistic Biophysical Techniques Reveal Structural Mechanisms of Engineered Cationic Antimicrobial Peptides in Lipid Model Membranes

In the quest for new antibiotics, two novel engineered cationic antimicrobial peptides (eCAPs) have been rationally designed. WLBU2 and D8 (all 8 valines are the d -enantiomer) efficiently kill both Gram-negative and -positive bacteria, but WLBU2 is toxic and D8 nontoxic to eukaryotic cells. We explore protein secondary structure, location of peptides in six lipid model membranes, changes in membrane structure and pore evidence. We suggest that protein secondary structure is not a critical determinant of bactericidal activity, but that membrane thinning and dual location of WLBU2 and D8 in the membrane headgroup and hydrocarbon region may be important. While neither peptide thins the Gram-negative lipopolysaccharide outer membrane model, both locate deep into its hydrocarbon region where they are primed for self-promoted uptake into the periplasm. The partially α-helical secondary structure of WLBU2 in a red blood cell (RBC) membrane model containing 50 % cholesterol, could play a role in destabilizing this RBC membrane model causing pore formation that is not observed with the D8 random coil, which correlates with RBC hemolysis caused by WLBU2 but not by D8.     

膜反应器在乙苯脱氢反应过程中的应用(英文)

以γ－Ａｌ２Ｏ３微孔陶瓷膜构成膜反应器（ＣＭＲ），使用ＧＳ－０５工业催化剂，在工业过程的操作条件下，研究了乙苯脱氢生产苯乙烯膜的反应规律。与工业上的固定康（ＰＦＲ）过程比较，有膜反应过程产率可提高５％－１０％。在本研究的条件下，股反应的优化实际上就是催化剂反应活性和膜渗透性的匹配。     

Study on a novel polyester composite nanofiltration membrane by interfacial polymerization of triethanolamine (TEOA) and trimesoyl chloride (TMC): I. Preparation, characterization and nanofiltration properties test of membrane

A novel thin-film composite (TFC) membrane for nanofiltration (NF) was developed by the interfacial polymerization of triethanolamine (TEOA) and trimesoyl chloride (TMC) on the polysulfone (PSf) supporting membrane. The active surface of the membrane was characterized by using FT-IR, XPS and SEM. The performance of TFC membrane was optimized by studying the preparation parameters, such as the reaction time of polymerization, pH of aqueous phase and the concentration of reactive monomers. It is found that the membrane performance is related to the changes of the monomer content in the aqueous phase rather than in the organic phase. Furthermore, the nanofiltration properties of the TFC membrane were tested by examining the separating performance of various salts at 0.6 MPa operating pressure. The rejection to different salt solutions decreased as per the order of Na₂SO₄ (82.2%), MgSO₄ (76.5%), NaCl (42.2%) and MgCl₂ (23%). Also, streaming potential tests indicated that isoelectric point of the TFC membrane is between pH 4 and 5. Moreover, the investigation of the flux for NaCl solution at different pH showed that the polyester NF composite membrane is also particularly suitable for treating acidic feeds: the flux increased from 8.4 to 11.5 L/m² h when pH of the feed decreased from 9 to 3. Additionally, the TFC membrane exhibits good long-term stability.