电流感生膜放电
Current-induced membrane discharge
摘要：
过限流（OLC）通过水溶液离子交换膜（超过扩散限制）的可能机制已经争论了半个世纪。最近在微流体实验中观察到了与电渗不稳定性（EOI）一致的流动，但现有的理论忽略了化学效应，仍有待定量检验。在这里，我们表明，电荷调节和水的自电离可以导致OLC的“电流诱导膜放电”（CIMD），即使在没有流体流动。盐耗尽导致大的电场，其排出水共离子，导致膜放电并失去其选择性。由于盐共离子和水离子有助于OLC，CIMD干扰电渗析（盐反离子去除），但可用于电流辅助离子交换和pH控制。CIMD还抑制了导致EOI的扩展空间电荷，因此在OLC的模型和实验中都应该重新考虑它。
英文摘要：
Possible mechanisms for over-limiting current (OLC) through aqueous ion-exchange membranes (exceeding diffusion limitation) have been debated for half a century. Flows consistent with electro-osmotic instability (EOI) have recently been observed in microfluidic experiments, but the existing theory neglects chemical effects and remains to be quantitatively tested. Here, we show that charge regulation and water self-ionization can lead to OLC by "current-induced membrane discharge" (CIMD), even in the absence of fluid flow. Salt depletion leads to a large electric field which expels water co-ions, causing the membrane to discharge and lose its selectivity. Since salt co-ions and water ions contribute to OLC, CIMD interferes with electrodialysis (salt counter-ion removal) but could be exploited for current-assisted ion exchange and pH control. CIMD also suppresses the extended space charge that leads to EOI, so it should be reconsidered in both models and experiments on OLC.
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