有机无机杂化膜的制备方法与应用研究

有机-无机杂化膜结合了有机膜和无机膜的优点,具备突出的分离性能、抗污染性能、机械性能以及物化稳定性能等。本文综述了有机-无机杂化膜的制备方法,并从气体分离、水处理和质子传导等领域论述了国内外杂化膜的应用。     

磷酸化二氧化硅填充磺化聚醚醚酮质子交换膜的制备及表征

制备了两种磷酸化改性的介孔二氧化硅亚微米球形颗粒,分别为仅外表面接枝磷酸根基团的颗粒(PMPS-Ⅰ)和内外表面均接枝磷酸根基团的颗粒(PMPS-Ⅱ)。颗粒具有均一的尺寸和规则排布的六面体一维贯通孔道。将制备的二氧化硅颗粒与磺化聚醚醚酮(SPEEK)溶液共混制备杂化膜。与填充PMPS-Ⅰ的杂化膜相比,填充PMPS-Ⅱ的杂化膜显示出较好的质子传导性能。当PMPS-Ⅱ的填充量为5%(质量)时,杂化膜在60℃、100%相对湿度下最高质子传导率为0.241 S·cm^-1。研究结果表明,连续贯通的质子传递通道有助于提高杂化膜的质子传导率。     

有机-无机杂化膜的制备与应用进展

介绍了有机-无机杂化膜的结构分类;系统阐述了溶胶-凝胶、原位聚合、直接分散及插层复合等杂化膜的制备方法;论述了杂化膜在气体分离、液体分离、质子传导以及膜反应器方面的应用。展望了杂化膜的未来发展方向,认为应研究杂化膜的成膜机理、制备条件及结构与性能关系、有机-无机2相间的相容性,研究新的杂化方法,以期制备性能更优异的杂化膜材料,并探索新的应用领域     

有机-无机杂化材料制备质子交换膜的研究进展

综述了近年来采用有机-无机杂化材料制备质子交换膜的研究进展，重点介绍了由掺入了质子导电单元或经过磺化的有机-无机杂化材料制得的质子交换膜及由带磺酸基的有机硅通过溶胶-凝胶工艺制备的有机-无机杂化质子材料制得的交换膜，并从制备方法出发分析了每种质子交换膜的性能。     

燃料电池用非氟复合质子交换膜的研究进展

介绍了几种非氟复合质子交换膜,包括有机-无机杂化材料质子交换膜(ORMOER)和基于聚苯并咪唑(PBI)、磺化聚醚醚酮(SPEEK)的复合质子交换膜,主要从制备方法出发分析了每种复合膜的优缺点以及在燃料电池(PEMFC)中的应用前景。     

燃料电池用有机-无机杂化质子交换膜的研究进展

质子交换膜燃料电池具有能量转化效率高、寿命长、比功率和比能量高、以及对环境友好等优点。质子交换膜则是关键部件之一,它起到分隔燃料和氧化剂、传导质子和绝缘电子的作用,其性能和寿命直接决定电池的性能和寿命。本文主要介绍了有机无机杂化质子交换膜的特点,并对近几年的发展状况进行了综述,就其设计原理、制备方法及优缺点作了简要评述。     

磷酸化二氧化硅填充磺化聚醚醚酮质子交换膜的制备及表征（英文）

制备了两种磷酸化改性的介孔二氧化硅亚微米球形颗粒,分别为仅外表面接枝磷酸根基团的颗粒(PMPS-Ⅰ)和内外表面均接枝磷酸根基团的颗粒(PMPS-Ⅱ)。颗粒具有均一的尺寸和规则排布的六面体一维贯通孔道。将制备的二氧化硅颗粒与磺化聚醚醚酮(SPEEK)溶液共混制备杂化膜。与填充PMPS-Ⅰ的杂化膜相比,填充PMPS-Ⅱ的杂化膜显示出较好的质子传导性能。当PMPS-Ⅱ的填充量为5%(质量)时,杂化膜在60℃、100%相对湿度下最高质子传导率为0.241 S·cm~(-1)。研究结果表明,连续贯通的质子传递通道有助于提高杂化膜的质子传导率。     

用于渗透汽化的有机—无机杂化膜研究进展

近年来,有机-无机杂化膜的研究受到学术界广泛关注,随着有机-无机杂化膜制备方法的多样化和分离性能的提高,其研究前景也越来越广阔。该文首先分析了有机-无机杂化膜相比于普通无机膜和有机膜在结构和性能上存在的优势,其次综述了有机-无机杂化膜的制备方法以及其在醇类、有机酸等有机溶剂或有机混合物中的分离提纯应用,重点讨论了其在渗透汽化中的应用。最后,对有机-无机杂化膜的研究前景进行展望。未来有机-无机杂化膜的研究应借助于新的计算工具,侧重于材料的选择或制备方法的改进,如探索具有多功能化学基团和具有明确层次结构的多孔填料的聚合物材料等,使有机-无机杂化膜具有更加广阔的应用前景。     

渗透汽化有机-无机杂化膜研究进展

近年来,有机-无机杂化膜的研究受到了广泛关注,随着有机-无机杂化膜制备方法的多样化和分离性能的提高,其研究前景也越来越广阔.该文首先分析了有机-无机杂化膜相比于普通无机膜和有机膜在结构和性能上存在的优势,其次综述了有机-无机杂化膜的制备方法以及其在醇类、有机酸等有机溶剂或有机混合物中的分离提纯应用,重点讨论了其在渗透汽化中的应用.最后,对有机-无机杂化膜的研究前景进行展望.未来有机-无机杂化膜的研究应借助于新的计算工具,侧重于材料的选择或制备方法的改进,如探索具有多功能化学基团聚合物材料和具有明确层次结构的多孔填料等.     

填充型有机-无机杂化分离膜研究进展

根据有机、无机组分间相互作用类型对有机-无机杂化膜进行了分类,重点论述了无机粒子填充型有机-无机杂化膜的最新研究进展,归纳了此类杂化膜的优异性能,总结了无机粒子的物理化学性能、含量、尺寸及其与聚合物的相容性等因素对此类杂化膜结构和性能的主要影响。最后提出了目前研究中存在的一些问题,并对其发展做出了简要的述评。     

Effect of cross-linking degree on proton conductivity of a Schiff-Base network impregnated with Brønsted acids

The cross-linking degree (crystallinity) and proton sources of conductors strongly impacts proton-conducting properties, but the attention is still limited, especially for covalent-organic frameworks. Here, we prepared a couple of cross-linking degrees of Schiff-Based Network by solvothermal (high surface specific area, SNW-S) and microwave-assisted (low cross-linking structure, SNW-M) strategies, respectively; subsequently, Brønsted acids (BAs)-entrapped Schiff-Based Network (SNW) composites as fillers are blended into polyvinyl pyrrolidone/poly(vinylidene fluoride) (PP) blends to form hybrid membranes. Varied crystalline degrees and microstructures of the SNWs are monitored by XRD, FTIR, and nitrogen adsorption, coupled with relevant conduction measurements like water uptake and proton conductivity (PC) for the composites and hybrid membranes. Structurally, under the aid of “acid–base pairs” between amine groups in Schiff-Based Network and Brønsted acids as proton carriers, the resulting H₂SO₄-incorporated SNW-M with poor cross-linking displays the high proton conductivity (4.96 × 10⁻³ S/cm) with an activation energy of 0.13 eV, whereas H₂SO₄ and H₃PO₄-incorporated SNW-S appear the relatively lower conductivities, imputable to the differences in the cross-linking degree of Schiff-Based Network and interactions between proton carriers and active sites in Schiff-Based Network. Additionally, the hybrid membranes also show σ values in the identical level of the composites, reaching to 8.02 × 10⁻³ S/cm at 323 K.     

Poly(vinyl alcohol)–polyacrylamide blends with cesium salts of heteropolyacid as a polymer electrolyte for direct methanol fuel cell applications

A class of inorganic–organic hybrid membranes with low methanol permeability characteristics for possible direct methanol fuel cell (DMFC) applications was architected, formulated, and fabricated through the blending of poly(vinyl alcohol) (PVA) and polyacrylamide (PAM) followed by crosslinking with glutaraldehyde (Glu). Cesium salts of different heteropolyacids, including phosphomolybdic acid (PMA), phosphotungstic acid (PWA), and silicotungstic acid (SWA), were incorporated into the polymer network to form corresponding hybrid membrane materials, namely, PVA–PAM–CsPMA–Glu, PVA–PAM–CsPWA–Glu, and PVA–PAM–CsSWA–Glu, respectively (where “Cs” together with a heteropolyacid abbreviation indicates the cesium salt of that acid). All the three hybrid polymer membranes fabricated exhibited excellent swelling, thermal, oxidative, and additive stability properties with desired proton conductivities in the range 10^?2 S/cm at 50% relative humidity. A dense network formation was achieved through the blending of PVA and PAM and by crosslinking with Glu, which led to an order of magnitude decrease in the methanol permeability compared to the state‐of‐the‐art commercial Nafion 115 membrane. The hybrid membrane containing CsSWA exhibited a very low methanol permeability (1.4 × 10^?8 cm²/s) compared to other membranes containing cesium salt of heteropolyacids such as PMA and PWA. The feasibility of these hybrid membranes as proton‐conducting electrolytes in DMFC was investigated, and the preliminary results were compared with those of Nafion 115. The results illustrate the attractive features and suitability of the fabricated hybrid membranes as an electrolyte for DMFC applications. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

In situ sol–gel route to novel sulfonated polyimide?SiO2 hybrid proton‐exchange membranes for direct methanol fuel cells

Polyimides (PIs) as high‐performance organic matrices are used in the preparation of PI composites because of their excellent mechanical, thermal and dielectric properties. The sol–gel method is a promising technique for preparing these PI composites due to the mild reaction conditions and the process being controllable. Although sulfonated polyimide (SPI) proton‐exchange membranes have attracted much attention recently, studies on preparing SPI‐based hybrid proton‐exchange membranes for fuel cells have been rare. A series of SPI? SiO₂ hybrid proton‐exchange membranes were prepared from amino‐terminated SPI pre‐polymers, 3‐glycidoxypropyltrimethoxysilane (KH‐560) and tetraethylorthosilicate through a co‐hydrolysis and condensation process using an in situ sol–gel method. The reactive silane KH‐560 was used to react with amino‐terminated SPI to form silane‐capped SPI in order to improve the compatibility between the polymer matrix and the inorganic SiO₂ phase. The microstructure and mechanical, thermal and proton conduction properties were studied in detail. The hybrid membranes were highly uniform without phase separation up to 30 wt% SiO₂. The storage modulus and tensile strength of the hybrid membranes increased with increasing SiO₂ content. The introduction of SiO₂ improved the methanol resistance while retaining good proton conductivity. The hybrid membrane with 30 wt% SiO₂ exhibited a proton conductivity of 10.57 mS cm^?1 at 80 °C and methanol permeability of 2.3 × 10^?6 cm² s^?1 possibly because the crosslinking structure and SiO₂ phases formed in the hybrids could retain water and were helpful to proton transport. Copyright © 2010 Society of Chemical Industry     

Proton Conductive Membranes from Covalently Cross-Linked Poly(Acrylate)/Silica Interpenetrating Networks

The preparation of hybrid proton conductive membranes that comprise of covalently linked interpenetrating polymer and inorganic networks is reported. The hybrid membranes are synthesized via simultaneous photo-initiated polymerization and sol–gel processing. The simultaneous processing permeates fabrication of the membranes that comprises covalently cross-linked polymeric and inorganic networks. The membranes are characterized by attenuated total reflectance-Fourier transform infrared spectroscopy, scaning electron microsopy, thermogravimetric analysis, differential scanning calorimetry, in order to confirm their chemical composition, structure, and morphology. An addition of 3-methacryloxypropyl trimethoxysilane into the sol–gel composition allows the formation of covalent linkages between polymeric and inorganic networks, which facilitates a uniform distribution of the molecular components across the fabricated membranes. The incorporation of the silica network leads to an increase in water retention and proton conductivity of hybrid membranes as compared to their purely polymeric analogues.     

磺化含酚酞侧基聚芳醚酮/氧化石墨烯复合质子交换膜的性能

采用共混制备了一系列磺化含酚酞侧基聚芳醚酮(SPEK-C)/氧化石墨烯(GO)复合质子交换膜,系统地研究了GO含量对复合膜性能的影响。结果表明,GO含量对膜的离子交换容量、稳定性、质子电导率和甲醇渗透率等有重要影响。复合膜质子电导率随GO含量增加而提高,GO含量为2%和5%的复合膜在80℃下质子电导率均在10^-1 S·cm^-1以上。80℃下,GO含量为5%的复合膜甲醇渗透率为6.69×10^-7 cm²·s^-1,低于同温度下复合前SPEK-C膜1个数量级。复合后膜的化学稳定性增强,离子交换容量和含水率均有提高,相对选择性明显增大,最高达SPEK-C的18.2倍。     

Solution‐blown SPEEK/POSS nanofiber–nafion hybrid composite membranes for direct methanol fuel cells

This study aims to develop novel hybrid composite membranes (NHMs) by impregnating Nafion solution into the porous sulfonated poly(ether ether ketone)/polyhedral oligomeric silsesquioxanes (SPEEK/POSS) nanofibers (NFs). The composite membrane was prepared by solution blowing of a mixture of SPEEK/POSS solution. The characteristics of the SPEEK/POSS NFs and the NHMs, including morphology, thermal stability, and performance of membrane as PEMs, were investigated. The performance of NHMs was compared with that of Nafion117 and SPEEK/Nafion composite membranes. Results showed that the introduction of POSS improved the proton conductivity, water swelling, and methanol permeability of membranes. A maximum proton conductivity of 0.163 S cm^?1 was obtained when the POSS content was 6 wt % at 80°C, which was higher than that of Nafion117 and SPEEK/Nafion. NHMs could be used as proton exchange membranes (PEMs) for fuel cell applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42843.     

Synthesis and properties of imidazole-grafted hybrid inorganic-organic polymer membranes

Imidazole rings were grafted on alkoxysilane with a simple nucleophilic substitute reaction to form hybrid inorganic-organic polymers with imidazole rings. Proton exchange membranes (PEM) based on these hybrid inorganic-organic polymers and H₃PO₄ exhibit high proton conductivity and high thermal stability in an atmosphere of low relative humidity. The grafted imidazole rings improved the proton conductivity of the membranes in the high temperature range. It is found that the proton conductivities increase with H₃PO₄ content and temperature, reaching 3.2 × 10⁻³ S/cm at 110 °C in a dry atmosphere for a membrane with 1 mole of imidazole ring and 7 moles of H₃PO₄. The proton conductivity increases with relative humidity (RH) as well, reaching 4.3 × 10⁻² S/cm at 110 °C when the RH is increased to about 20%. Thermogravimetric analysis (TGA) indicates that these membranes are thermally stable up to 250 °C in dry air, implying that they have a good potential to be used as the membranes for high-temperature PEM fuel cells.