Most electrochemical processes, such as electrodialysis, are limited by diffusion, but in porous media, surface conduction and electroosmotic flow also contribute to ionic flux. In this article, we report experimental evidence for surface-driven overlimiting current (faster than diffusion) and deionization shocks (propagating salt removal) in a porous medium. The apparatus consists of a silica glass frit (1 mm thick with a 500 nm mean pore size) in an aqueous electrolyte (CuSO4 or AgNO3) passing ionic current from a reservoir to a cation-selective membrane (Nafion). The current-voltage relation of the whole system is consistent with a proposed theory based on the electroosmotic flow mechanism over a broad range of reservoir salt concentrations (0.1 mM to 1.0 M) after accounting for (Cu) electrode polarization and pH-regulated silica charge. Above the limiting current, deionized water (≈10 μM) can be continuously extracted from the frit, which implies the existence of a stable shock propagating against the flow, bordering a depleted region that extends more than 0.5 mm across the outlet. The results suggest the feasibility of shock electrodialysis as a new approach to water desalination and other electrochemical separations.
1Rising global demand for potable water is driving innovation in water treatment 2 methods. Shock electrodialysis is a recently proposed technique that exploits deioniza-3 tion shock waves in porous media to purify water. In this letter, we present the first 4 continuous and scalable shock electrodialysis system and demonstrate the separation 5 of sodium, chloride, and other ions from a feed stream. Our prototype continuously 6 removes over 99% (and up to 99.99%) of salt from diverse electrolytes over a range 7 of concentrations (1 mM, 10 mM, and 100 mM). The desalination data collapses with 8 dimensionless current, scaled to charge advection in the feed stream. Enhanced water 9 recovery with increasing current (up to 79%) is a fortuitous discovery, which we at-
The development of energy and infrastructure efficient water purification systems are among the most critical engineering challenges facing our society. Water purification is often a multistep process involving filtration, desalination, and disinfection of a feedstream. Shock electrodialysis (shock ED) is a newly developed technique for water desalination, leveraging the formation of ion concentration polarization (ICP) zones and deionization shock waves in microscale pores near to an ion selective element. While shock ED has been demonstrated as an effective water desalination tool, we here present evidence of other simultaneous functionalities. We show that, unlike electrodialysis, shock ED can thoroughly filter micron-scale particles and aggregates of nanoparticles present in the feedwater. We also demonstrate that shock ED can enable disinfection of feedwaters, as approximately 99% of viable bacteria (here E. coli) in the inflow were killed or removed by our prototype. Shock ED also separates positive from negative particles, contrary to claims that ICP acts as a virtual barrier for all charged particles. By combining these functionalities (filtration, separation and disinfection) with deionization, shock ED has the potential to enable more compact and efficient water purification systems.2
Shock electrodialysis is a recently developed electrochemical water treatment method that shows promise for water deionization and ionic separations. Although simple models and scaling laws have been proposed, a predictive theory has not yet emerged to fit experimental data and enable system design. Here, we extend and analyze existing “leaky membrane” models for the canonical case of a steady shock in crossflow, as in recent experimental prototypes. Two‐dimensional numerical solutions are compared with analytical boundary‐layer approximations and experimental data. The boundary‐layer theory accurately reproduces the simulation results for desalination, and both models predict the data collapse of the desalination factor with dimensionless current, scaled to the incoming convective flux of cations. The numerical simulation also predicts the water recovery increase with current. Nevertheless, neither approach can quantitatively fit the transition from normal to over‐limiting current, which suggests gaps in our understanding of extreme electrokinetic phenomena in porous media.
The Debye-Hückel formula for ionic activity coefficients is extended for concentrated solutions by solving a simple model of many-body Coulomb correlations and adding the Born solvation energy. Given the bulk permittivity, our formula is able to fit activity data for diverse electrolytes with only one parameter to adjust the correlation length, which interpolates between the Bjerrum length and the mean ion spacing. The results show that ionic activity in most electrolytes is dominated by three types of electrostatic forces: (i) mean-field charge screening, (ii) solvation, and (iii) Coulomb correlations, both "over-screening" (charge oscillations) and "under-screening" (extending beyond the Debye screening length).
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