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Ion-exchange membranes (IEMs) are widely used in water, energy, and environmental applications, but transport models to accurately simulate ion permeation are currently lacking. This study presents a theoretical framework to predict ionic conductivity of IEMs by introducing an analytical model for condensed counterion mobility to the Donnan-Manning model. Modeling of condensed counterion mobility is enabled by the novel utilization of a scaling relationship to describe screening lengths in the densely charged IEM matrices, which overcame the obstacle of traditional electrolyte chemistry theories breaking down at very high ionic strength environments. Ionic conductivities of commercial IEMs were experimentally characterized in different electrolyte solutions containing a range of mono-, di-, and trivalent counterions. Because the current Donnan-Manning model neglects the mobility of condensed counterions, it is inadequate for modeling ion transport and significantly underestimated membrane conductivities (by up to ≈5× difference between observed and modeled values). Using the new model to account for condensed counterion mobilities substantially improved the accuracy of predicting IEM conductivities in monovalent counterions (to as small as within 7% of experimental values), without any adjustable parameters. Further adjusting the power law exponent of the screen length scaling relationship yielded reasonable precision for membrane conductivities in multivalent counterions. Analysis reveals that counterions are significantly more mobile in the condensed phase than in the uncondensed phase because electrostatic interactions accelerate condensed counterions but retard uncondensed counterions. Condensed counterions still have lower mobilities than ions in bulk solutions due to impedance from spatial effects. The transport framework presented here can model ion migration a priori with adequate accuracy. The findings provide insights into the underlying phenomena governing ion transport in IEMs to facilitate the rational development of more selective membranes. 

In a circular nutrient economy, nitrogen and phosphorous are removed from waste streams and captured as valuable fertilizer products, to more sustainably reuse the resources in closed-loops and simultaneously protect receiving aquatic environments from harmful N and P emissions. For nutrient reclamation to be competitive with the existing practices of N fixation and P mining, the methods of recovery must achieve at least comparable energy consumption. This study employed the Gibbs free energy of separation to quantify the minimum energy required to recover various N and P fertilizer products from waste streams of fresh and hydrolyzed urine, greywater, domestic wastewater, and secondary treated wastewater effluent. The comparative advantages in theoretical energy intensities for N and P recovery from nutrient-dense waste streams, such as fresh and hydrolyzed urine, were assessed against the other more dilute sources. For example, compared to reclaiming the nutrients from treated wastewater effluent at centralized wastewater treatment plants, the minimum energy required to recover 1.0 M NH 3(aq) from source-separated hydrolyzed urine can be ≈40–68% lower, whereas recovering KH 2 PO 4(s) from diverted fresh urine can, in principle, be ≈13–34% less energy intensive. The study also evaluated the efficiencies required by separation techniques for the energy demand of N and P recovery to be lower than the current production approaches of the Haber–Bosch process and phosphate rock mining. For instance, the most energetically favorable ammoniacal nitrogen and orthophosphate reclamation schemes, which target hydrolyzed and fresh urine, respectively, require energy efficiencies >7% and >39%. This study highlights that strategic selection of waste stream and fertilizer product can enable the most expedient recovery of nutrients and realize a circular economy model for N and P management. 

Seawater electrolysis is an attractive approach for producing clean hydrogen fuel in scenarios where freshwater is scarce and renewable electricity is abundant. However, chloride ions (Cl−) in seawater can accelerate electrode corrosion and participate in the undesirable chlorine evolution reaction (CER). This problem is especially acute in acidic conditions that naturally arise at the anode as a result of the desired oxygen evolution reaction (OER). Herein, we demonstrate that ultrathin silicon oxide (SiOx) overlayers on model platinum anodes are highly effective at suppressing the CER in the presence of 0.6 M Cl− in both acidic and unbuffered pH-neutral electrolytes by blocking the transport of Cl− to the catalytically active buried interface while allowing the desired oxygen evolution reaction (OER) to occur there. The permeability of Cl− in SiOx overlayers is 3 orders of magnitude less than that of Cl− in a conventional salt-selective membrane used in reverse osmosis desalination. The overlayers also exhibit robust stability over 12 h in chronoamperometry tests at moderate overpotentials. SiOx overlayers demonstrate a promising step toward achieving selective and stable seawater electrolysis without the need to adjust the pH of the electrolyte. 

Solar-thermal desalination (STD) is a potentially low-cost, sustainable approach for providing high-quality fresh water in the absence of water and energy infrastructures. Despite recent efforts to advance STD by improving heat-absorbing materials and system designs, the best strategies for maximizing STD performance remain uncertain. To address this problem, we identify three major steps in distillation-based STD: (i) light-to-heat energy conversion, (ii) thermal vapor generation, and (iii) conversion of vapor to water via condensation. Using specific water productivity as a quantitative metric for energy efficiency, we show that efficient recovery of the latent heat of condensation is critical for STD performance enhancement, because solar vapor generation has already been pushed toward its performance limit. We also demonstrate that STD cannot compete with photovoltaic reverse osmosis desalination in energy efficiency. We conclude by emphasizing the importance of factors other than energy efficiency, including cost, ease of maintenance, and applicability to hypersaline waters.