Membrane technologies using reverse osmosis (RO) and nanofiltration (NF) have been widely implemented in water purification and desalination processes. Separation between species at the molecular level is achievable in RO and NF membranes due to a complex and poorly understood combination of transport mechanisms that have attracted the attention of researchers within and beyond the membrane community for many years. Minimizing existing knowledge gaps in transport through these membranes can improve the sustainability of current water-treatment processes and expand the use of RO and NF membranes to other applications that require high selectivity between species. Since its establishment in 1949, and with growing popularity in recent years, Eyring’s transition-state theory (TST) for transmembrane permeation has been applied in numerous studies to mechanistically explore molecular transport in membranes including RO and NF. In this review, we critically assess TST applied to transmembrane permeation in salt-rejecting membranes, focusing on mechanistic insights into transport under confinement that can be gained from this framework and the key limitations associated with the method. We first demonstrate and discuss the limited ability of the commonly used solution-diffusion model to mechanistically explain transport and selectivity trends observed in RO and NF membranes. Next, we review important milestones in the development of TST, introduce its underlying principles and equations, and establish the connection to transmembrane permeation with a focus on molecular-level enthalpic and entropic barriers that govern water and solute transport under confinement. We then critically review the application of TST to explore transport in RO and NF membranes, analyzing trends in measured enthalpic and entropic barriers and synthesizing new data to highlight important phenomena associated with the temperature-dependent measurement of the activation parameters. We also discuss major limitations of the experimental application of TST and propose specific solutions to minimize the uncertainties surrounding the current approach. We conclude with identifying future research needs to enhance the implementation and maximize the benefit of TST application to transmembrane permeation.

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Membrane technologies that enable the efficient purification of impaired water sources are needed to address growing water scarcity. However, state-of-the-art engineered membranes are constrained by a universal, deleterious trade-off where membranes with high water permeability lack selectivity. Current membranes also poorly remove low–molecular weight neutral solutes and are vulnerable to degradation from oxidants used in water treatment. We report a water desalination technology that uses applied pressure to drive vapor transport through membranes with an entrapped air layer. Since separation occurs due to a gas-liquid phase change, near-complete rejection of dissolved solutes including sodium chloride, boron, urea, and N -nitrosodimethylamine is observed. Membranes fabricated with sub-200-nm-thick air layers showed water permeabilities that exceed those of commercial membranes without sacrificing salt rejection. We also find the air-trapping membranes tolerate exposure to chlorine and ozone oxidants. The results advance our understanding of evaporation behavior and facilitate high-throughput ultraselective separations.

Desalination technologies using salt-rejecting membranes are a highly efficient tool to provide fresh water and augment existing water supplies. In recent years, numerous studies have worked to advance a variety of membrane processes with different membrane types and driving forces, but direct quantitative comparisons of these different technologies have led to confusing and contradictory conclusions in the literature. In this Review, we critically assess different membrane-based desalination technologies and provide a universal framework for comparing various driving forces and membrane types. To accomplish this, we first quantify the thermodynamic driving forces resulting from pressure, concentration, and temperature gradients. We then examine the resistances experienced by water molecules as they traverse liquid- and air-filled membranes. Last, we quantify water fluxes in each process for differing desalination scenarios. We conclude by synthesizing results from the literature and our quantitative analyses to compare desalination processes, identifying specific scenarios where each process has fundamental advantages.

Pressure-driven distillation is a separation process in which hydraulic pressure is used to drive water vapor transport across an air-trapping porous hydrophobic membrane. Current development of pressure-driven distillation is limited by a lack of robust, large-area membranes. Here, we report desalination using pressure-driven vapor transport through scalable polymeric polytetrafluorethylene membranes. The membranes showed pressure-driven water flow with near-complete rejection of sodium chloride (greater than 99%) under hydraulic pressures of up to 10.3 bar. Membrane structure, surface chemistry, and desalination performance were found to be unaffected by doses of sodium hypochlorite up to 3000 ppm h. Flux decline due to biofouling from Pseudomonas aeruginosa bacterium was effectively mitigated using chlorine. Membranes also exhibited high temperature resilience with operation up to 60 °C. Overall, this work demonstrates the use of large-area polymeric materials in pressure-driven distillation and highlights key advantages in chlorine and heat tolerance.