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1.229 V. This lower onset voltage is likely due to either other reactions that start at a lower potential, such as the oxidation of chloride ions to hypochlorite ions, also occurring or the low partial pressures of hydrogen and oxygen gas, since no gases are being supplied to the electrode channels, causing the electrolysis potential to shift to a lower value. The behavior at overlimiting current for the curve for the bare silica frit showed a linear increase in current with an overlimiting conductivity (slope × thickness of frit) of 9.79×10−3 S/m. This behavior is not only qualitatively consistent with previous experimental data [22, 43, 70] and theoretical predictions [25, 24], but also quantitatively consistent with prior experiments with the same silica glass frit and the same membrane [22], in which this behavior was attributed to electro- osmotic surface convection. The nonlinear increase at very high currents can likely be explained by water splitting and concentration polarization in the electrode stream, which is similar to what happens in traditional electrodialysis [84, 77, 76]. At even higher currents (above 11 A/m2 (> 50jlim)), bubble formation becomes significant and can be observed in the effluent from the electrode streams, causing the voltage to become unstable. In order to demonstrate the importance of surface transport in the porous medium in the overlimiting current regimes, we also show a plot of a polarization curve for a positively charged silica glass frit (blue line), whose surfaces had been treated using layer-by-layer deposition of the positively charged polymer polydiallyldimethylammonium chloride (pDADMAC) [22, 43], in addition to the curve for the bare silica glass frit (black line). The two curves diverge significantly in the part of the overlimiting regime in which strong desalination is observed for the bare frit. The point of divergence is above the theoretical diffusion-limited current (jlim = 2zeDeffc0/L ≈ 0.18 A/m2 for 10 mM NaCl, where Deff = 4.01×10−10 m2/s and L = 4.3 mm), likely due to convection [22]. 2.3.2 Desalination After characterizing the device using IV curves, desalination tests were conducted to evaluate its efficacy. These tests were conducted with four different electrolytes over a range of two orders of magnitude in concentration, three different flow rates, and 55PDF Image | Shock Electrodialysis for Water Purification and Electrostatic Correlations
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