Large-Area 2D Covalent Organic Framework Membranes with Tunable Single-Digit Nanopores for Predictable Mass Transport.

The potential of covalent organic frameworks (COFs) for molecular separations remains unrealized because of challenges transforming nanoscale COF materials into large-area functional COF membranes. Herein, we report the synthesis of large-area (64 cm2), ultrathin (24 nm), ß-ketoenamine-linked 2D COFs using a facile interfacial polymerization technique. Angstrom-level control over single-digit nanopore size (1.4-2.0 nm) is achieved by direct integration of variable-length monomers. We apply these techniques to fabricate a series of large-area 2D COF membranes with variable thicknesses, pore sizes, and supporting materials. Tunable 2D COF properties enable control over COF membrane mass transport, resulting in high solvent fluxes and sharp molecular weight cutoffs. For organic solvent nanofiltration, the 2D COF membranes demonstrate an order-of-magnitude greater permeance than the state-of-the-art commercial polymeric membrane. We apply continuum models to quantify the dominance of pore passage resistance to mass transport over pore entrance resistance. A strong linear correlation between single-digit nanopore tortuosity and 2D COF thickness enables solvent fluxes to be predicted directly from solvent viscosity and COF membrane properties. Solvent-nanopore interactions characterized by the membrane critical interfacial tension also appear to influence mass transport. The pore flow transport model is validated by predicting the flux of a 52 nm thick COF membrane.

Characterizing salt permeability in polyamide desalination membranes using electrochemical impedance spectroscopy.

Improving the performance of desalination membranes requires better measurements of salt permeability in the polyamide separating layer to elucidate the thermodynamic and kinetic components of membrane permselectivity. In this work, electrochemical impedance spectroscopy (EIS) is introduced as a technique to measure the salt permeability and estimate the salt partition coefficient in thin polyamide films created using molecular layer-by-layer deposition. The impedance of supported polyamide films ranging in thickness from 3.5 nm to 28.5 nm were measured in different electrolyte solutions. Impedance spectra were modeled with equivalent circuits containing resistive and capacitive elements associated with the EIS measurement system as well as characteristic low-frequency parallel resistive and capacitive elements that are associated with the polyamide film. The characteristic polyamide membrane resistance increases with film thickness, decreases with solution concentration, and is an order of magnitude greater for a divalent cationic solution than for a monovalent cationic solution. For each polyamide film, salt permeability is calculated from the membrane resistance, and a salt partition coefficient is estimated. At the highest solution concentration measured, which is representative of brackish water desalination conditions, the calculated salt permeabilities range from P s = 1.3 × 10-16 m s-1 to 3.9 × 10-16 m s-1, and the estimated salt partition coefficients range from K s = 0.008 to 0.016. These measurements demonstrate that EIS is a powerful tool for studying membrane permselectivity through the measurement of salt permeability in thin polyamide films.

Studying water and solute transport through desalination membranes via neutron radiography.

Neutron radiography, a non-destructive imaging technique, is applied to study water and solute transport through desalination membranes. Specifically, we use neutron radiography to quantify lithium chloride draw solute concentrations across a thin-film composite membrane during forward osmosis permeation. This measurement provides direct visual confirmation of incomplete support layer wetting and reveals significant dilutive external concentration polarization of the draw solution outside of the membrane support layer. These transport-limiting phenomena have been hypothesized in previous work and are not accounted for in the standard thin-film model of forward osmosis permeation, resulting in inaccurate estimations of membrane transport properties. Our work demonstrates neutron radiography as a powerful measurement tool for studying membrane transport and emphasizes the need for direct experimental measurements to refine the forward osmosis transport model.

Effect of Final Monomer Deposition Steps on Molecular Layer-by-Layer Polyamide Surface Properties.

A current challenge to desalination membrane technology is the inability to precisely control the properties of the polyamide selective layer due to the complexity of interfacial polymerization. In this study, we investigate the ability of molecular layer-by-layer (mLbL) assembly, an alternative polyamide fabrication technique, to create polyamide surfaces with tunable chemistry. We explore the influence of terminating monomer, monomer deposition time, monomer size, and the presence of underlying ionizable functional groups on mLbL-derived polyamide surface properties. AFM colloidal probe measurements, contact angle titrations, QCM cesium adsorption experiments, and XPS data show that polyamide films terminated with m-phenylenediamine or trimesoyl chloride for 20-30 s are chemically similar. Increasing terminating monomer deposition time or using a smaller, more reactive monomer results in more distinct colloidal-probe adhesive interactions, contact angle titration curves, negative charge densities, and near surface atomic compositions. By optimizing the final monomer deposition steps, both amine-rich and carboxyl-rich polyamide surfaces can be fabricated, which has implications for the application of mLbL assembly to membrane-based desalination.

Membrane scaling and flux decline during fertiliser-drawn forward osmosis desalination of brackish groundwater.

Fertiliser-drawn forward osmosis (FDFO) desalination has been recently studied as one feasible application of forward osmosis (FO) for irrigation. In this study, the potential of membrane scaling in the FDFO process has been investigated during the desalination of brackish groundwater (BGW). While most fertilisers containing monovalent ions did not result in any scaling when used as an FO draw solution (DS), diammonium phosphate (DAP or (NH4)2HPO4) resulted in significant scaling, which contributed to severe flux decline. Membrane autopsy using scanning electron microscopy (SEM), energy-dispersive x-ray spectroscopy (EDS), and x-ray diffraction (XRD) analysis indicated that the reverse diffusion of DAP from the DS to the feed solution was primarily responsible for scale formation during the FDFO process. Physical cleaning of the membrane with deionised water at varying crossflow velocities was employed to evaluate the reversibility of membrane scaling and the extent of flux recovery. For the membrane scaled using DAP as DS, 80-90% of the original flux was recovered when the crossflow velocity for physical cleaning was the same as the crossflow velocity during FDFO desalination. However, when a higher crossflow velocity or Reynolds number was used, the flux was recovered almost completely, irrespective of the DS concentration used. This study underscores the importance of selecting a suitable fertiliser for FDFO desalination of brackish groundwater to avoid membrane scaling and severe flux decline.

In situ surface chemical modification of thin-film composite forward osmosis membranes for enhanced organic fouling resistance.

Forward osmosis (FO) is an emerging membrane-based water separation process with potential applications in a host of environmental and industrial processes. Nevertheless, membrane fouling remains a technical obstacle affecting this technology, increasing operating costs and decreasing membrane life. This work presents the first fabrication of an antifouling thin-film composite (TFC) FO membrane by an in situ technique without postfabrication treatment. The membrane was fabricated and modified in situ, grafting Jeffamine, an amine-terminated poly(ethylene glycol) derivative, to dangling acyl chloride surface groups on the nascent polyamide active layer. Surface characterization by contact angle, Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), zeta potential, atomic force microscopy (AFM), and fluorescence microscopy, confirms the presence of Jeffamine on the membrane surface. We demonstrate the improved fouling resistance of the in situ modified membranes through accelerated dynamic fouling FO experiments using a synthetic wastewater feed solution at high concentration (250 mg/L) of alginate, a model macromolecule for the hydrophilic fraction of wastewater effluent organic matter. Our results show a significantly lower flux decline for the in situ modified membranes compared to pristine polyamide (14.3 ± 2.7% vs 2.8 ± 1.4%, respectively). AFM adhesion force measurements between the membrane and a carboxylate-modified latex particle, a surrogate for the organic (alginate) foulant, show weaker foulant-membrane interactions, further confirming the enhanced fouling resistance of the in situ modified membranes.

Desalination and reuse of high-salinity shale gas produced water: drivers, technologies, and future directions.

In the rapidly developing shale gas industry, managing produced water is a major challenge for maintaining the profitability of shale gas extraction while protecting public health and the environment. We review the current state of practice for produced water management across the United States and discuss the interrelated regulatory, infrastructure, and economic drivers for produced water reuse. Within this framework, we examine the Marcellus shale play, a region in the eastern United States where produced water is currently reused without desalination. In the Marcellus region, and in other shale plays worldwide with similar constraints, contraction of current reuse opportunities within the shale gas industry and growing restrictions on produced water disposal will provide strong incentives for produced water desalination for reuse outside the industry. The most challenging scenarios for the selection of desalination for reuse over other management strategies will be those involving high-salinity produced water, which must be desalinated with thermal separation processes. We explore desalination technologies for treatment of high-salinity shale gas produced water, and we critically review mechanical vapor compression (MVC), membrane distillation (MD), and forward osmosis (FO) as the technologies best suited for desalination of high-salinity produced water for reuse outside the shale gas industry. The advantages and challenges of applying MVC, MD, and FO technologies to produced water desalination are discussed, and directions for future research and development are identified. We find that desalination for reuse of produced water is technically feasible and can be economically relevant. However, because produced water management is primarily an economic decision, expanding desalination for reuse is dependent on process and material improvements to reduce capital and operating costs.