新颖无机质子传导材料的研究进展

质子传导在燃料电池、气体传感及电致显色等领域有重要的研究前景.尤其是在燃料电池领域,由于其具有低污染、高效率、操作简单和寿命长等优点而被广泛应用.本文介绍了质子传导在质子交换膜燃料电池中的重要作用及工作原理,分析了质子交换膜的质子传导机理,并简要分析总结了近年来关于无机及其复合质子导体材料的研究进展.     

直接甲醇燃料电池用聚合物质子交换膜的研究进展

对各种类型的聚合物质子交换膜,如全氟磺酸聚合物、部分氟化磺酸聚合物、非氟磺酸聚合物、有机-无机复合质子交换膜的结构、性质以及最新的研究进展进行了综述.并且,对该领域未来的发展进行了展望.     

燃料电池用高温质子交换膜

与传统质子交换膜燃料电池相比,高温质子交换膜燃料电池(HT-PEMFCs)不仅可以提高催化剂对CO的耐受能力,还能简化水热管理,提高能量转化效率。高温质子交换膜是实现高温操作的关键部件之一。掺杂无机磷酸的高温质子交换膜因为在高温度(100~200 ℃)和低相对湿度下具有较高的质子传导率,以及较长使用寿命而成为研究的热点。高的磷酸掺杂量有助于质子传导率的提升,但也会牺牲膜的机械强度,因此已有大量致力于提升膜综合性能的改性研究。本文对目前基于磷酸基的聚苯并咪唑类、聚芳醚类等高温质子交换膜的改性策略进行评述,并梳理总结了包括 MOFs、COFs 在内的新型多孔材料在质子交换膜领域的应用,最后指出了高温质子交换膜当前面临的挑战。     

一种新型结构质子交换膜的研究

质子导体的研究近年来受到了广泛的关注，具有质子传导能力的电解质材料可广泛地应用于燃料电池、电解池、电化学反应装置以及传感器等领域，特别是作为质子交换膜燃料电池（PEMFC）的核心组件之一的质子交换膜越来越受到人们的重视。Nafion（Du Pont）全氟磺酸膜是目前广泛用于PEMFC中的一种质子导体。Nafion全氟磺酸膜具有优异的化学稳定性以及在较低温度条件下高的质子电导率，然而其高昂的价格、差的高温性能以及用于直接甲醇燃料电池（DMFC）中时的高甲醇渗透率阻碍了DMFC商业化发展。     

质子交换膜燃料电池有序化膜电极

质子交换膜燃料电池的核心部件--膜电极经历了两代传统制备方法后,已经进入第三代有序化膜电极发展阶段.有序化膜电极包括质子导体有序化膜电极和电子导体有序化膜电极两大类,而电子导体有序化膜电极包括催化剂材料有序化膜电极和催化剂载体材料有序化膜电极.有序化膜电极具有良好的电子、质子、水和气体等多相物质传输通道,从而可以大大降低膜电极中Pt载量、提升燃料电池的发电性能和延长燃料电池寿命.本文整理了近几年有关有序化膜电极的研究报道,梳理了有序化膜电极研究进展,归纳比较了各种有序化膜电极制备方法的优缺点,对未来高性能、低成本和长寿命的膜电极制备技术开发具有指导意义.     

质子交换膜燃料电池膜电极耐久性的提升

质子交换膜燃料电池由于具有能量转换效率高、操作温度低、环境友好等优点而备受人们关注。随着2014年丰田发布燃料电池电动汽车Mirai,带来了新一轮燃料电池及燃料电池汽车的产业化热潮。然而,提升质子交换膜燃料电池的寿命,开发新一代长寿命燃料电池膜电极及燃料电池仍然是本领域的挑战性课题。膜电极(MEA)是质子交换膜燃料电池最核心的部件,其耐久性直接决定着燃料电池的寿命。MEA主要由质子交换膜、催化剂层、气体扩散层三部分组成。本文从质子交换膜、催化剂及载体、气体扩散层三个方面介绍了近年来国内外在提升燃料电池膜电极的寿命(耐久性)方面所做的工作,并对未来的相关研究和发展做了述评及展望。     

金属有机框架材料在质子交换膜燃料电池中的潜在应用

金属有机框架亦称作多孔配位网状结构,是一种多孔晶态材料,具有结构可设计、孔壁可功能化修饰、高度晶态化、比表面积大及优良的导电性等诸多优点,使其在能源转换及储存方面备受关注。本文详细介绍了新型金属有机框架质子导体及电催化剂在燃料电池方面的相关研究;综述了国内外近年来在金属有机框架质子交换膜和氧还原电催化领域所取得的一些重要进展,例如金属有机框架质子交换膜电导率可高达1.82 S·cm^-1（70℃,90% RH）,金属有机框架电催化剂作为阴极在膜电极测试中可产生0.91 W·cm^-2（0.6 V）的峰值功率密度;并指出了金属有机框架在质子交换膜和电催化剂研究中存在的问题,这为今后开发高电导性质子交换膜和高催化活性电催化提供了新思路。     

静电纺丝制备质子交换膜燃料电池催化剂层综述

质子交换膜燃料电池催化剂层在成本、耐久性以及性能上的局限是制约燃料电池汽车商业化的瓶颈. 已有文献证明静电纺丝技术制备的纳米纤维催化剂层能提高催化剂利用率、增加三相界面和三相通道以及提高耐久性. 作者结合所在课题组的工作综述了静电纺丝技术制备质子交换膜燃料电池催化剂层的研究进展. 首先,介绍了质子交换膜燃料电池催化剂层的发展历程,并从制备方式和结构两个方面对其进行分类和总结;接下来,从静电纺丝纳米纤维催化剂层的制备、物理特性表征、电化学性能分析及耐久性表征等方面进行了总结;最后,从三相界面、三相通道以及量产适用性的视点比较了三种结构的催化剂层,介绍了质子交换膜燃料电池催化剂层的发展趋势,并梳理了静电纺丝法制备质子交换膜燃料电池催化剂层领域待研的问题.     

质子交换膜燃料电池催化剂稳定化方法研究进展

催化剂稳定性是制约质子交换膜燃料电池商业化的两个主要障碍之一,因此增强燃料电池催化剂稳定性研究一直是该领域的热点问题。本文从纳微尺度、原子分子水平的认识出发,分析催化剂衰减机理,评估催化剂稳定化研究所面临的问题,综述近年来质子交换膜燃料电池催化剂稳定化方法,提出进一步增强催化剂稳定性的发展方向。     

燃料电池用跨温区质子交换膜材料研究进展

质子交换膜燃料电池(PEMFC)是一种电化学能量转换器件，能将燃料中的化学能转换为电能，具有高效、清洁、寿命长等优点，可应用于动力电池、固定式和便携式电源等领域。质子交换膜(PEM)是其中的关键部件，主要用于隔离阴阳两极和传递质子等。但当前质子交换膜燃料电池的发展面临着成本高、寿命不足等挑战。本文结合近年的研究热点，从质子传输机制出发将质子交换膜燃料电池分为磺酸功能化PEM和磷酸掺杂型PEM两大类，从主链结构的差异以及改性方法等方面综述近年来的研究进展，详细介绍了材料的化学结构、膜材料性能、电化学性能等，并针对现存的一些问题和不足对质子交换膜燃料电池今后的发展方向进行了展望。     

Water uptake and infrared absorption in SrZr<Subscript>0.95</Subscript>M<Subscript>0.05</Subscript>O<Subscript>3-</Subscript><Subscript>a</Subscript> (<Emphasis Type="Italic">M</Emphasis>=Ga,Sc, Y and Nd)

Summary Proton concentration in SrZr_0.95M_0.05O_3-α (M=Ga, Sc, Y and Nd) was measured with a thermobalance at different temperatures (T=673-973 K) and water vapor pressures (P_H2O=0.9-12.8 kPa). At all the pressures and temperatures examined, the amount of proton concentration in these samples is in the order of Sc>Y>Ga>Nd. By an equilibrium evaluation, we estimated the maximum possible proton concentration about 2.0 mol% in these samples. Infrared (IR) absorption spectra are measured in these samples. The absorption bands can be fitted by four (M=Ga, Y, Nd) or three (M=Sc) Gaussian bands.     

Proton mobility in hydrates of inorganic acids and acid salts

Published data on the mechanisms of hydrogen ion transport in solids and aqueous solutions are described systematically, including defect formation, rotational mobility of proton-containing groups, proton hopping along a hydrogen bond, proton translational mobility, and proton conduction. Resorting to the authors" theoretical results and published data, the main criteria for the selection of systems possessing high proton mobility are formulated.     

基于杂多酸的固体高质子导体*

杂多酸固体高质子导体在燃料电池、传感器和电显色装置等方面具有潜在的应用前景。本文概述了杂多酸的质子导电性,归纳了其质子导电性的一些规律,以表格形式列举了各类杂多酸的电导率。将不同质量分数的杂多酸固载在各类固体基质上,可以对杂多酸质子导电材料改性以便于工业中实际应用。这些杂化材料兼有杂多酸的高质子导电性以及基质的稳定性与机械延展性。本文综述了近几年来新型杂多酸,杂多酸-无机基质复合材料,杂多酸-有机基质复合材料,杂多酸-多元基复合材料的质子电导率、稳定性、结构形态等等方面的研究进展,详细介绍了杂多酸在质子交换膜燃料电池中的应用,并对杂多酸固体高质子导体的应用前景进行了展望。     

On stability and protonation of multielectron systems: The concept of proton affinity. II. Dissociative proton attachment and protonation—Deprotonation mapping

A few touches on the thematic palette “molecular protonation” directly linked to the concept of molecular stability have been accomplished. They are of different nature, of different origin, and taken from “different angles” of lighting; however, together, they definitely provide a sufficiently complete picture “The protonation interaction, as being strong enough, may break the stability of molecules subject to protonation.” © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012     

细胞色素c氧化酶研究新进展

综述了细胞色素c氧化酶研究的新进展,重点评述了细胞色素c氧化酶晶体结构和各种谱学研究结果,质子传递途径、O2还原的催化机理以及与其相耦联的质子泵机理等方面的最新进展。     

Synthesis and properties of novel polyimides from sulfonated binaphthalene dianhydride for proton exchange membranes

A sulfonated dianhydride monomer, 6,6′‐disulfonic‐4,4′‐binaphthyl‐1,1′,8,8′‐tetracarboxylic dianhydride (SBTDA), was successfully synthesized by direct sulfonation of the parent dianhydride, 4,4′‐binaphthyl‐1,1′,8,8′‐tetracarboxylic dianhydride (BTDA), using fuming sulfuric acid as the sulfonating reagent. A series of sulfonated homopolyimides were prepared from SBTDA and various common nonsulfonated diamines. The resulting polymer electrolytes, which contain ion conductivity sites on the deactivated positions of the aryl backbone rings, displayed high proton conductivities of 0.25–0.31 S cm^?1 at 80 °C. The oxidative stability test indicated that the attachment of the ? SO₃H groups onto the dianhydride units did not deteriorate the oxidative stability of the SPI membranes. The better membranes were achieved by the copolymerization of nonsulfonated diamine, SBTDA, and BTDA. Copolymer membrane synthesized from hexane‐1,6‐diamine, SBTDA, and BTDA displayed excellent water stability of more than 1000 h at 90 °C, while its proton conductivity was still at a high level (comparable to that of Nafion 117). Furthermore, the novel block copolymer ( II‐b ) displayed higher proton conductivity compared with the random one ( II‐r ) obviously, probably due to the slightly higher water uptake and better microphase separated morphology. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2820–2832, 2008     

Intra- and intermolecular proton transfer reactions in 2-phenyl substituted benzazoles

The present review describes the salient features of inter- and intramolecular proton transfer reactions of 2-(2′-aminophenyl)-, 2-(3′-aminophenyl)-, 2-(4′-aminophenyl)-, 2-(2′-hydroxyphenyl)-, 2-(3′-hydroxyphenyl)- and 2-(4′-hydroxyphenyl)-benzimidazoles, benzoxazoles and benzothiazoles. Fluorescence quantum yield of the phototautomer produced by the intramolecular hydrogen bonding decreases on going from benzimidazole to benzoxazole to benzothiazole. This indicates that the rate of internal conversion increases in the order of compounds as mentioned above. The biprotonic phototautomerism or the presence of intermolecular proton transfer has led to the formation of (i) nonfluorescent zwitterions in case of hydroxyphenyl derivatives and the ground state precursor of this species in neutral molecules, (ii) nonfluorescent monoanions from fluorescent monoanions and (iii) nonfluorescent monocations from monocations in case of aminophenyl derivatives. In the case of 2-(4′-aminophenyl)-substituted compounds, the first protonation has always led to the formation of two types of monocations; one by protonating the amino group and the other by protonating the tertiary nitrogen atom. The former is more stable in aqueous media and the latter in non-polar media.     

Synthesis and Characterization of Sulfonated Polyimides Containing Trifluoromethyl Groups as Proton Exchange Membranes

A novel sulfonated diamine, 4,4′‐bis(4‐amino‐3‐trifluoromethylphenoxy) biphenyl 3,3′‐disulfonic acid (F‐BAPBDS), was successfully synthesized by nucleophilic aromatic substitution of 4,4′‐dihydroxybiphenyl with 2‐chloro‐5‐nitrobenzotrifluoride, followed by reduction and sulfonation. A series of sulfonated polyimides of high molecular weight (SPI‐x, x represents the molar percentage of the sulfonated monomer) were prepared by copolymerization of 1,4,5,8‐naphathlenetetracarboxylic dianhydride (NTDA) with F‐BAPBDS and nonsulfonated diamine. Flexible and tough membranes of high mechanical strength were obtained by solution casting and the electrolyte properties of the polymers were intensively investigated. The copolymer membranes exhibited excellent oxidative stability due to the introducing of the CF₃ groups. The SPI membranes displayed desirable proton conductivity (0.52×10⁻¹–0.97×10⁻¹ S·cm⁻¹) and low methanol permeability (less than 2.8×10⁻⁷ cm²·s⁻¹). The highest proton conductivity (1.89×10⁻¹ S·cm⁻¹) was obtained for the SPI‐90 membrane at 80°C, with an IEC of 2.12 mequiv/g. This value is higher than that of Nafion 117 (1.7×10⁻¹ S·cm⁻¹). Furthermore, the hydrolytic stability of the obtained SPIs is better than the BDSA and ODADS based SPIs due to the hydrophobic CF₃ groups which protect the imide ring from being attacked by water molecules, in spite of its strong electron‐withdrawing behaviors.     

Excited-state proton transfer from pyranine to acetate in methanol

Excited-state proton transfer (ESPT) of pyranine (8-hydroxypyrene-1,3,6-trisulphonate, HPTS) to acetate in methanol has been studied by steady-state and time-resolved fluorescence spectroscopy. The rate constant of direct proton transfer from pyranine to acetate (k ₁) is calculated to be ∼1 × 10⁹ M⁻¹ s⁻¹. This is slower by about two orders of magnitude than that in bulk water (8 × 10¹⁰ M⁻¹ s⁻¹) at 4 M acetate.