Proton acceptors

  • 文章类型: Journal Article
    最近,据报道,几丁质和壳聚糖表现出高质子传导性,并在燃料电池中充当电解质。特别是,值得注意的是,水合几丁质中的质子传导率比水合壳聚糖中的质子传导率高30倍。由于燃料电池电解质需要更高的质子传导率,从微观角度阐明实现更高的质子传导的关键因素对于燃料电池的未来发展至关重要。因此,我们从微观角度使用准弹性中子散射(QENS)测量了水合几丁质中的质子动力学,并比较了水合几丁质和壳聚糖之间的质子传导机理。QENS结果表明,即使在238K下,甲壳质中的一部分氢原子和水合水也是移动的,流动的氢原子及其扩散随着温度的升高而增加。发现几丁质中移动质子的扩散常数比壳聚糖中的扩散常数大两倍,停留时间快两倍。此外,实验结果表明,可解离氢原子在几丁质和壳聚糖之间的转变过程是不同的。为了在水合壳聚糖中实现质子传导,水合氢离子(H3O+)的氢原子应转移到另一个水合水中。相比之下,在水合几丁质中,氢原子可以直接转移到邻近几丁质的质子受体。可以推断,与水合壳聚糖相比,水合甲壳质中的质子电导率更高,这是由于扩散常数和氢原子动力学的停留时间以及质子受体的位置和数量的差异。
    Recently, it was reported that chitin and chitosan exhibited high-proton conductivity and function as an electrolyte in fuel cells. In particular, it is noteworthy that proton conductivity in the hydrated chitin becomes 30 times higher than that in the hydrated chitosan. Since higher proton conductivity is necessary for the fuel cell electrolyte, it is significantly important to clarify the key factor for the realization of higher proton conduction from a microscopic viewpoint for the future development of fuel cells. Therefore, we have measured proton dynamics in the hydrated chitin using quasi-elastic neutron scattering (QENS) from the microscopic viewpoint and compared the proton conduction mechanism between hydrated chitin and chitosan. QENS results exhibited that a part of hydrogen atoms and hydration water in chitin are mobile even at 238 K, and the mobile hydrogen atoms and their diffusion increase with increasing temperature. It was found that the diffusion constant of mobile protons is two times larger and that the residence time is two times faster in chitin than that in chitosan. In addition, it is revealed from the experimental results that the transition process of dissociable hydrogen atoms between chitin and chitosan is different. To realize proton conduction in the hydrated chitosan, the hydrogen atoms of the hydronium ions (H3O+) should be transferred to another hydration water. By contrast, in hydrated chitin, the hydrogen atoms can transfer directly to the proton acceptors of neighboring chitin. It is deduced that higher proton conductivity in the hydrated chitin compared with that in the hydrated chitosan is yielded by the difference of diffusion constant and the residence time by hydrogen-atom dynamics and the location and number of proton acceptors.
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  • 文章类型: Journal Article
    目前工作的主要重点是研究苯乙酰胺如何与有机溶剂中的其他分子相互作用。利用红外光谱获得了18种溶剂中CO基团的频率。溶剂的经验参数为受体数(AN),范德华相互作用参数(SVW)和线性溶剂化能关系(LSER)与苯乙酰胺的羰基拉伸振动(ν(CO))的频率相关,以估计分子间相互作用的贡献。结果表明,溶剂对苯乙酰胺的CO拉伸振动频率有明显的影响。烷醇的自缔合导致O-H-O=C氢键强度的增强和ν(CO)峰的红移。苯乙酰胺的ν(CO)更容易受到溶剂氢键供体酸度的影响。这项研究有助于彻底了解液体混合物中的分子相互作用和微观结构。
    The main attention of present work is to study how benzeneacetamide interacts with other molecules in organic solvents. The frequencies of CO groups in 18 solvents were obtained by using infrared spectroscopy. The empirical parameters of the solvents as the acceptor number (AN), the van der Waals interaction parameters (SVW) and the linear solvation energy relationships (LSER) were correlated with the frequencies of carbonyl stretching vibration (ν(CO)) of benzeneacetamide to estimate the contributions in intermolecular interactions. The results showed that solvent effects on the frequencies of CO stretching vibrations of benzeneacetamide were obvious. Self-association of alkanol leads to enhancement of O-H⋯O=C hydrogen bond strength and red-shift of the ν(CO) peak. The ν(CO) of benzeneacetamide is more vulnerable to the acidity of the hydrogen bond donor of the solvent. This research contributes to a thorough understanding of the molecular interactions and microstructures in the liquid mixtures.
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  • 文章类型: Journal Article
    In the present work, the thermochemistry of solution, solvation, and hydrogen bonding of cyclic amides in proton acceptor (B) and proton donor (RXH) solvents were studied. The infinite dilution solution enthalpies of δ-valerolactam, N-methylvalerolactam, ε-caprolactam, and N-methylcaprolactam were measured at 298.15 K. The solvation enthalpies of cyclic amides were calculated based on the measured solution enthalpies and sublimation/vaporization enthalpies from literature. The enthalpies of hydrogen bonding between cyclic amides and proton acceptor and donor solvents were then calculated as a difference between the total solvation enthalpy and the non-specific contribution. The latter was estimated via two different approaches in proton donor and proton accepting solvents. The effect of the cycle size on the strength of hydrogen bonding of the cyclic amides in solution is discussed.
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