多孔活性炭孔径分布的表征

总结了利用气体吸附法表征多孔活性炭中孔和微孔孔径分布的各种方法。BJH方法和MP模型忽略了微孔内势能叠加效应,仅适合描述中孔孔径分布;HK模型和以Dubinin填充理论为基础的各种方法,考虑了微观下势能叠加的效果,在一定程度上能很好地描述微孔孔径分布;最近围绕GAI(GeneralizedAdsorptionIsotherm)而展开的利用密度范函理论(DFT,densityfunctiontheory)和巨正则系综蒙特卡罗(GCMC,grandcanonicalensemblemontecarlo)模拟确定微孔孔径分布的方法较好地克服了Dubinin理论中存在的缺点,是较好的两种方法,但其有效性还需要更多的实验结果来证明。     

有序介孔氧化硅膜的制备及结构研究

本文介绍了在α-Al₂O₃中空纤维载体上制备担载有序氧化硅膜的方法。应用LXRD、HRTEM、TG-DTA、SEM、氮气吸附等测试手段对膜的结构、形貌进行了表征。LXRD和HRTEM结果显示所制备的非担载膜具有高度有序的二维六方结构。SEM分析发现担载膜表面完整、无缺陷。气体渗透实验表明中空纤维担载膜具有一定的气体选择性，在0.1 MPa下对H₂/N₂和CH₄/N₂的分离因子分别为2.80和1.65，气体透过膜孔的扩散由努森机制所控制。等温氮气吸附实验显示：500 ℃热处理后非担载膜的比表面积为548.84 m²·g^-1，孔容为0.57 mL·g^-1。     

Enhanced electrochemical properties of a novel polyvinyl formal membrane supporting gel polymer electrolyte by Al2O3 modification

Polyvinyl formal (PVFM)‐based dense polymer membranes with nano‐Al₂O₃ doping are prepared via phase inversion method. The membranes and also their performances as gel polymer electrolytes (GPEs) for lithium ion battery are studied by field emission scanning electron microscope, X‐ray diffraction, differential scanning calorimetry, mechanical strength test, electrolyte uptake test, electrochemical impedance spectroscopy, cyclic voltammetry, and charge–discharge test. The polymer membrane with 3 wt % nano‐Al₂O₃ doping shows the improved mechanical strength of 12.16 MPa and electrolyte uptake of 431.25% compared with 10.47 MPa and 310.59% of the undoped sample, respectively. The membrane absorbs and swells liquid electrolyte to form stable GPE with ionic conductivity of 4.92 × 10^?4 S cm^?1 at room temperature, which is higher than 1.77 × 10^?4 S cm^?1 of GPE from the undoped membrane. Moreover, the Al₂O₃‐modified membrane supporting GPE exhibits wide electrochemical stability window of 1.2–4.8 V (vs. Li/Li⁺) and good compatibility with LiFePO₄ electrode, which implies Al₂O₃‐modified PVFM‐based GPE to be a promising candidate for lithium ion batteries. © 2014 Wiley Periodicals, Inc. J. Polym. Sci. Part B: Polym. Phys. 2014 , 52, 572–577     

Effect of chemical functionalization on the mechanical properties of polypropylene hollow fiber membranes

Chemical treatment of polymeric hollow fiber membranes (HFMs) is used to prepare their exterior surfaces for coatings. Typical treatments can cleave both C? C and C? H bonds of polypropylene, leading to lower mechanical strength of the fibers. This study evaluated the yield strength, maximum strain, ultimate tensile strength, and burst strength of HFMs treated with each of three common oxidizing reagents: ozone as a gas phase system, aqueous solutions of potassium persulfate, and ammonium persulfate for liquid phase systems. The yield strength and ultimate tensile strength of HFMs decreased continuously with increasing ozonation time. Batch treatments with aqueous oxidizing systems showed limiting values of the yield and ultimate tensile strengths with time. Swelling the hollow fibers with methanol prior to oxidation caused less reduction of the mechanical properties after persulfate treatment. Fibers pretreated with methanol showed lower losses of mechanical properties strength with aqueous oxidation systems. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1366–1373     

Artificial Iono‐ and Photosensitive Membranes Based on an Amphiphilic Aza‐Crown‐Substituted Hemicyanine

Artificial iono‐ and photosensitive membranes based on an amphiphilic aza‐crown‐substituted hemicyanine are assembled on liquid and solid supports and their aggregation behaviour, which is influenced by the binding of metal cations and surface density, is studied. The photoinduced charge‐transfer properties of an analogous non‐amphiphilic hemicyanine in solution are also demonstrated. An asymmetric sandwich dimer model is proposed and existence of such dimers in solution is evidenced by transient absorption and fluorescence anisotropy experiments. Changes in absorption and emission spectra, as well as compression isotherms of the amphiphile observed in the presence of cations, are discussed in terms of 2D molecular reorganisation. Surface‐pressure‐controlled reversible excimer formation at the air–water interphase and excimer‐type emission of Langmuir–Blodgett films in the presence of cations are demonstrated and are discussed on the basis of fibre‐optic fluorimetry and fluorescence microscopy results.     

Synthesis of a nano‐sized chiral imprinted polymer and its use as an (S)‐atenolol carrier in the bulk liquid membrane

In this work, nanosized chiral imprinted polymers containing (S)‐atenolol ((S)‐ATN) selective sites were synthesized by using suspension polymerization in silicon oil. (S)‐ATN, methacrylic acid, and ethylene glycol dimethacrylate were used as enantiomerically pure template, functional monomer, and cross‐linker, respectively. The prepared chiral imprinted polymers were used as the carrier elements in a bulk liquid membrane (BLM). (S)‐ATN transport capability of the chiral imprinted polymers was compared with that of the nonimprinted polymer. It was shown that chiral imprinted polymers could transport (S)‐ATN through the BLM more effectively than (R)‐ATN, whereas no difference in the facilitated transport was observed between (R)‐ATN and (S)‐ATN when using nonimprinted polymer particles as the carrier element in the BLM. A kinetic model was proposed for the transportation of (S)‐ATN through the chiral imprinted polymers based BLM. It was found that the extraction of ATN from the source to the membrane controls the chiral separation process. It was also found that the pH of source and receiving phases as well as the racemic ATN concentration in source phase had very crucial effect on the chiral separation efficiency.     

Ultrathin pH‐Sensitive Nanoporous Membranes for Superfast Size‐Selective Separation

Stimuli‐responsive nanoporous membranes have attracted increasing interest in various fields due to their abrupt changes of permeation/separation in response to the external environment. Here we report ultrathin pH‐sensitive nanoporous membranes that are easily fabricated by the self‐assembly of poly(acrylic acid) (PAA) in a metal hydroxide nanostrand solution. PAA‐adsorbed nanostrands (2.5–5.0 nm) and PAA‐Cu^II nanogels (2.0–2.5 nm) grow competitively during self‐assembly. The PAA‐adsorbed nanostrands are deposited on a porous support to fabricate ultrathin PAA membranes. The membranes display ultrafast water permeation and good rejection as well as significant pH‐sensitivity. The 28 nm‐thick membrane has a water flux decrease from 3740 to 1350 L m^?1 h^?1 bar^?1 (pH 2.0 to 7.0) with a sharp decrease at pH 5.0. This newly developed pH‐sensitive nanoporous membranes may find a wide range of applications such as controlled release and size‐ and charge‐selective separation.     

Visualization and Quantification of Transmembrane Ion Transport into Giant Unilamellar Vesicles

Transmembrane ion transporters (ionophores) are widely investigated as supramolecular agents with potential for biological activity. Tests are usually performed in synthetic membranes that are assembled into large unilamellar vesicles (LUVs). However transport must be followed through bulk properties of the vesicle suspension, because LUVs are too small for individual study. An alternative approach is described whereby ion transport can be revealed and quantified through direct observation. The method employs giant unilamellar vesicles (GUVs), which are 20–60 μm in diameter and readily imaged by light microscopy. This allows characterization of individual GUVs containing transporter molecules, followed by studies of transport through fluorescence emission from encapsulated indicators. The method provides new levels of certainty and relevance, given that the GUVs are similar in size to living cells. It has been demonstrated using a highly active anion carrier, and should aid the development of compounds for treating channelopathies such as cystic fibrosis.     

A Carbon–Air Battery for High Power Generation

We report a carbon–air battery for power generation based on a solid‐oxide fuel cell (SOFC) integrated with a ceramic CO₂‐permeable membrane. An anode‐supported tubular SOFC functioned as a carbon fuel container as well as an electrochemical device for power generation, while a high‐temperature CO₂‐permeable membrane composed of a CO₃^2? mixture and an O^2? conducting phase (Sm_0.2Ce_0.8O_1.9) was integrated for in situ separation of CO₂ (electrochemical product) from the anode chamber, delivering high fuel‐utilization efficiency. After modifying the carbon fuel with a reverse Boudouard reaction catalyst to promote the in situ gasification of carbon to CO, an attractive peak power density of 279.3 mW cm^?2 was achieved for the battery at 850 °C, and a small stack composed of two batteries can be operated continuously for 200 min. This work provides a novel type of electrochemical energy device that has a wide range of application potentials.     

Remarkably Enhanced Gas Separation by Partial Self‐Conversion of a Laminated Membrane to Metal–Organic Frameworks

Separation methods based on 2D interlayer galleries are currently gaining widespread attention. The potential of such galleries as high‐performance gas‐separation membranes is however still rarely explored. Besides, it is well recognized that gas permeance and separation factor are often inversely correlated in membrane‐based gas separation. Therefore, breaking this trade‐off becomes highly desirable. Here, the gas‐separation performance of a 2D laminated membrane was improved by its partial self‐conversion to metal–organic frameworks. A ZIF‐8‐ZnAl‐NO₃ layered double hydroxide (LDH) composite membrane was thus successfully prepared in one step by partial conversion of the ZnAl‐NO₃ LDH membrane, ultimately leading to a remarkably enhanced H₂/CH₄ separation factor and H₂ permeance.