质子交换膜燃料电池零下冷启动研究

在零下启动过程中,质子交换膜燃料电池阴极中氧气还原反应生成的水会在催化剂层内部结冰,因而阻碍氧气传输,覆盖催化剂层反应活性位点,降低电化学活性面积,影响燃料电池发电性能,甚至会导致零下启动失败;同时,结冰/融化循环还会破坏膜电极结构,影响燃料电池寿命。因此,质子交换膜燃料电池零下启动技术的研究对促进燃料电池汽车的推广应用有重要意义。本文针对质子交换膜燃料电池的零下启动过程,从实验研究、机理解释、模型分析及策略开发等角度对文献内容进行了梳理,并对涉及质子交换膜燃料电池零下启动过程的专利技术进行了总结。     

质子交换膜燃料电池零下冷启动研究进展

在零下启动过程中,质子交换膜燃料电池阴极氧气还原反应生成的水会在催化剂层内部结冰,因而阻碍氧气传输,覆盖催化剂层反应活性位点,降低电化学活性面积,影响燃料电池发电性能,甚至会导致零下启动失败;同时,结冰/融化循环还会破坏膜电极结构,影响燃料电池寿命。因此,质子交换膜燃料电池零下启动技术的研究对促进燃料电池汽车的推广应用有重要意义。本文针对质子交换膜燃料电池的零下启动过程,从实验研究、机理解释、模型分析及策略开发等角度对文献进行了综述分析,并对涉及质子交换膜燃料电池零下启动过程的专利技术进行了总结。     

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。     

质子交换膜燃料电池铂电催化剂稳定策略

质子交换膜燃料电池使用寿命低是制约其商业化应用的主要瓶颈. 其中,影响质子交换膜燃料电池寿命的一个主要因素是其所广泛使用的贵金属铂基电催化剂在燃料电池苛刻的运行环境下（如可变电压、强酸性、气液两相流等）容易发生降解,导致电催化剂性能衰减,从而降低了质子交换膜燃料电池的使用寿命. 因此,如何保持铂基电催化剂的电化学稳定性已成为质子交换膜燃料电池稳定性研究中的重大科学问题. 本论文基于作者在该领域的长期研究成果,评述了应用于质子交换膜燃料电池的铂电催化剂稳定性的研究进展. 重点关注了能够大幅改善铂催化剂电化学稳定性的策略,包括聚合物稳定策略、多孔碳封装/限域稳定策略以及载体稳定策略,并对这些铂催化剂稳定策略所面临的挑战进行了展望.     

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.     

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.     

高性能高功率密度质子交换膜燃料电池膜电极

膜电极是质子交换膜燃料电池最为重要的核心部件,其性能直接决定着燃料电池的性能。提高膜电极的性能和功率密度,对于推动燃料电池的商业化进程具有十分重要的意义。通常意义上的膜电极包括质子交换膜、阴极催化层、阳极催化层、阴极气体扩散层和阳极气体扩散层等5个基本单元(常常称之为五合一膜电极),气体扩散层又包括气体扩散材料层和微孔整平层;膜电极的性能取决于材料和制备技术两个方面,制备技术、膜电极的关键组成材料、铂载量都对膜电极的性能和功率密度具有重要影响。近年来,随着催化剂和质子交换膜等关键材料性能的提升,以及制备技术的进步,国内外膜电极的性能得到了大幅度的提升,丰田公司燃料电池的体积功率密度可高达3.2 kW/L。本文将主要从膜电极制备技术的角度(涉及催化剂层和气体扩散层的制备技术等)介绍近年来高性能高功率密度膜电极的研究发展情况,同时介绍国内外在降低膜电极铂载量和开发自增湿膜电极方面的研究进展。     

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。     

高性能质子交换膜燃料电池

用全氟碘酸质子交换膜作为质子交换膜燃料电池（ＰＥＭＦＣ）电解质,简化了水和电解质的管理。本文研究了该燃料电池质子交换膜厚度对电池性能影响;性能最佳的Ｎａｆｉｏｎ１１２膜和低铂载量Ｅ－ＴＥＫ电极组装的ＰＥＭＦＣ,在输出功率高达０．９５Ｗ／ｃｍ＾２;同时考察了电池的能量转换效率、Ｅ－ＴＥＫ电极中铂电催化剂利用率和电池的稳定性。     

质子交换膜燃料电池Pd修饰Pt/C催化剂的电催化性能

通过对Pt催化剂表面进行Pd修饰提高质子交换膜燃料电池阴极催化剂的氧还原反应(ORR)活性. 采用乙二醇还原法制备了不同比例的Pd修饰Pt/C催化剂. 透射电镜(TEM)和X射线衍射(XRD)测试结果表明, 制备的催化剂贵金属颗粒粒径主要分布在1.75～2.50 nm之间, 并均匀地分散在碳载体表面. 循环伏安方法(CV)研究表明Pd修饰Pt/C催化剂的电化学活性面积低于传统的Pt/C催化剂. 但通过旋转圆盘电极(RDE)测试研究发现, 制备的催化剂具有比传统Pt/C催化剂高的ORR活性.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.     

Synthesis of N-substituted carbazolones from α-iodo enaminones via Pd(0)-catalyzed intramolecular coupling under microwave irradiation

A variety of N-aryl and N-alkyl carbazolones were conveniently achieved in good to high yields via Pd₂(dba)₃-mediated intramolecular coupling of N-substituted α-iodo enaminones under microwave irradiation. The Pd(0)-catalyzed cyclization was found to proceed favorably with the more electron-deficient phenyl ring during the reactions involving unsymmetrical N,N-diaryl α-iodo enaminones. This unique property enables the construction of carbazolone skeleton containing nitro substituted benzenoid ring.     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Synthesis of substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles by intramolecular nitrilimine cycloaddition

Both substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles have been synthesized by the 3+2 intramolecular dipolar cycloaddition of nitrilimines to alkynes. This cyclization has been extended to more versatile 3-bromo derivatives by the use of alkynylbromides as dipolarophiles.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.