Deterioration of Aqueous n-Octanoate Electrolysis with Electrolytic Conductivity Collapse Caused by the Formation of n-Octanoic Acid/n-Octanoate Agglomerates
Deterioration of Aqueous n-Octanoate Electrolysis with Electrolytic Conductivity Collapse Caused by the Formation of n-Octanoic Acid/n-Octanoate Agglomerates
复制标题
DOI：
10.1002/celc.201700069
复制
发表时间：
2017-06-01
期刊：
影响因子：
4
通讯作者：
Harnisch, Falk
中科院分区：
文献类型：
--
作者：
Urban, Carolin;Harnisch, Falk
在水（作为绿色溶剂）中进行的有机电合成具有利用可再生能源选择性生产化学品的潜力。然而，有机分子的有限溶解度阻碍了它们的水电解。对于所提出的平台化学正辛酸/正辛酸盐（均概括为C-8），表明只要满足某些要求，C-8的水电解可以成功进行。事实证明，电极附近经常被忽视的局部 pH 值变化会导致大的 C-8 团聚物（例如囊泡、双层）的形成，从而使电解电导率最小化，从而恶化电解。需要强调的是，对于 C-8 电解，必须优先选择 pH 缓冲电解质而不是 pH 中性支持电解质，以实现更高的时空产率。循环伏安法、通过动态光散射进行粒度分析以及光学显微镜表征了这些附聚物的性质。
Electroorganic synthesis performed in water (as a green solvent) bears potential for the selective production of chemicals from renewable power. Yet, the limited solubility of organic molecules hampers their aqueous electrolysis. For the proposed platform chemical n-octanoic acid/n-octanoate, both summarized as C-8, it is shown that the aqueous electrolysis of C-8 can be performed successfully, provided that certain requirements are fulfilled. It is evidenced that the often-overlooked local pH shift in the proximity of the electrode can lead to the formation of large C-8 agglomerates (e.g. vesicles, bilayers), which deteriorate the electrolysis by minimizing the electrolytic conductivity. It is stressed that pH-buffering electrolytes have to be preferred to pH-neutral supporting electrolytes for C-8 electrolysis to achieve improved space-time yields. Cyclic voltammetry, particle-size analysis through dynamic light scattering, and light microscopy characterize the nature of these agglomerates.