Inhibiting Polyamide Intrusion of Thin Film Composite Membranes: Strategies and Environmental Implications.

Thin film composite polyamide (TFC) nanofiltration (NF) membranes represent extensive applications at the water-energy-environment nexus, which motivates unremitting efforts to explore membranes with higher performance. Intrusion of polyamide into substrate pores greatly restricts the overall membrane permeance because of the excessive hydraulic resistance, while the effective inhibition of intrusion remains technically challenging. Herein, we propose a synergetic regulation strategy of pore size and surface chemical composition of the substrate to optimize selective layer structure, achieving the inhibition of polyamide intrusion effective for the membrane separation performance enhancement. Although reducing the pore size of the substrate prevented polyamide intrusion at the intrapore, the membrane permeance was adversely affected due to the exacerbated "funnel effect". Optimizing the polyamide structure via surface chemical modification of the substrate, where reactive amino sites were in situ introduced by the ammonolysis of polyethersulfone substrate, allowed for maximum membrane permeance without reducing the substrate pore size. The optimal membrane exhibited excellent water permeance, ion selectivity, and emerging contaminants removal capability. The accurate optimization of selective layer is anticipated to provide a new avenue for the state-of-the-art membrane fabrication, which opens opportunities for promoting more efficient membrane-based water treatment applications.

The stabilization of ultrafiltration membrane blended with randomly structured amphiphilic copolymer: Micropollutants adsorption properties in filtration processes.

In this study, a blend membrane consisting of polyvinylidene fluoride (PVDF) and tertiary amine containing random copolymer poly(methyl methacrylate-r-dimethylamino-2-ethyl methacrylate) (P(MMA-r-DMAEMA)) was fabricated and utilized as an adsorptive membrane for micropollutants (anionic dye and heavy metal ions) removal from aqueous solutions. Cross-linking the random copolymer by p-xylylene dichloride (XDC) produced the membrane with improved copolymer retention ratio and stability, while slightly variated physicochemical properties. Besides, the fluxes of crosslinked blend membranes dramatically increased from 0.7 ± 0.1 L/(m2h) to 118.6 ± 5.9 L/(m2h). Then the present blend membrane was carried out adsorption and filtration experiments to investigate the influence of various of operation parameters including initial solution pH value, contacting time, initial solution concentration, and recycling efficiency on micropollutants removal. The experimental results showed that the removal of the anionic dyes and heavy metal ions on this tertiary amine containing blend membrane was a pH-dependent process with the maximum adsorption capacity at the initial solution pH of 3.5 for anionic dyes and 6.0 for metal ions, respectively. The membrane showed highly efficient capture of sunset yellow (above 99%). Meanwhile, the captured sunset yellow was recovered and concentrated with a small volume of alkaline solutions at pH 10.0, which simultaneously regenerated the membrane for its reuse. In a 3-cycle capture-recovery test, the membrane demonstrated a high sunset yellow recovery ratio and a volumetric concentration ratio as high as 400%. Our study provides an alternative strategy for functionalized membrane fabrication, micropollutants removal and recovery.

Nanofiltration for drinking water treatment: a review.

In recent decades, nanofiltration (NF) is considered as a promising separation technique to produce drinking water from different types of water source. In this paper, we comprehensively reviewed the progress of NF-based drinking water treatment, through summarizing the development of materials/fabrication and applications of NF membranes in various scenarios including surface water treatment, groundwater treatment, water reuse, brackish water treatment, and point of use applications. We not only summarized the removal of target major pollutants (e.g., hardness, pathogen, and natural organic matter), but also paid attention to the removal of micropollutants of major concern (e.g., disinfection byproducts, per- and polyfluoroalkyl substances, and arsenic). We highlighted that, for different applications, fit-for-purpose design is needed to improve the separation capability for target compounds of NF membranes in addition to their removal of salts. Outlook and perspectives on membrane fouling control, chlorine resistance, integrity, and selectivity are also discussed to provide potential insights for future development of high-efficiency NF membranes for stable and reliable drinking water treatment.

Hollow nanosphere construction of covalent organic frameworks for catalysis: (Pd/C)@TpPa COFs in Suzuki coupling reaction.

A novel catalyst with a yolk-shell structure was designed to overcome the leaching of noble metals in heterogeneous catalysis. Through a template method, palladium (Pd) nanoparticles were encapsulated by hollow spherical covalent organic frameworks (COFs) consisting of 2,4,6-trihydroxybenzene-1,3,5-tricarbaldehyde (Tp) and p-phenylenediamine (Pa). The final catalyst with a yolk-shell structure was denoted as (Pd/C)@TpPa COFs. The unique morphology and chemical structure of this novel composite (Pd/C)@TpPa COFs were confirmed by a transmission electron microscope (TEM), a laser particle analyzer, X-ray diffraction (XRD), and N2 adsorption and desorption. Subsequently, to demonstrate its catalytic performance brought by structural design, this novel catalyst was applied to catalyze the Suzuki reaction. Interestingly, this catalyst exhibited a brilliant size cutoff efficiency for aryl benzene amounting to 100% and achieved a high conversion with only 0.05 mol% Pd loading. Besides, this catalyst could be readily recovered via filtration and reused for at least five consecutive cycles without any significant loss in its activity.

Dissecting the Role of Substrate on the Morphology and Separation Properties of Thin Film Composite Polyamide Membranes: Seeing Is Believing.

Recent studies show that the surface morphology of a thin film composite (TFC) polyamide membrane depends strongly on its porous substrate. Nevertheless, the underlining mechanisms and the effects on membrane separation performance remain controversial. To dissect the exact role of pore properties, we synthesized TFC polyamide membranes on polycarbonate substrates with cylindrical track-etched pores (PCTE) of well-defined pore size ranging from 10 to 800 nm. Leaf-like roughness features were most prominent for polyamide films formed on substrates of intermediate pore sizes (80 and 100 nm). Smaller pores inhibited leaf-like features as a result of insufficient storage of m-phenylenediamine (MPD) monomers for the interfacial reaction, whereas larger pores resulted in diminished surface roughness due to the lack of confinement to the interfacially degassed nanobubbles. Substrate porosity plays a critical role on membrane water permeability, while smaller pores with greater pore density are favored to improve membrane rejection. TFC polyamide membranes prepared on sponge-like poly(ether sulfone) and polysulfone substrates exhibit better water permeability and salt rejection compared to the PCTE-TFC membranes thanks to the simultaneously enhanced confinement and MPD storage effects. The mechanistic insights gained in this study reveal the huge potential of substrate design toward high-performance TFC RO membranes.

Tailoring Polyamide Rejection Layer with Aqueous Carbonate Chemistry for Enhanced Membrane Separation: Mechanistic Insights, Chemistry-Structure-Property Relationship, and Environmental Implications.

Surface roughness and the associated nanosized voids inside the roughness structures have great influence on the separation performance of thin film composite polyamide reverse osmosis (RO) membranes. Inspired by the recent findings that these voids are formed due to the degassing of CO2 nanobubbles during interfacial polymerization, we systematically investigated the role of carbonate chemistry, particularly the solubility of CO2, in the aqueous m-phenylenediamine (MPD) solution for the first time. "Ridge-and-valley" roughness features were obtained when the pH of the MPD solution was between the two acidity constants of the carbonate system (i.e., 6.3 ≤ pH ≤ 10.3), under which condition HCO3- dominates over the other carbonate species. Increasing pH over this range led to both increased water permeability and better rejection of various solutes, thanks to the simultaneously enhanced effective filtration area and cross-linking degree of the polyamide layer. Further increase of pH to 12.5 resulted in more disparate rejection results due to membrane hydrolysis: rejection of neural solutes (B and As(III)) was compromised whereas that of charged solutes (NaCl and As(V)) was maintained. The mechanistic insights gained in the current study reveal the critical need to design RO membranes directly for end applications based on first principles.

One-step tailoring surface roughness and surface chemistry to prepare superhydrophobic polyvinylidene fluoride (PVDF) membranes for enhanced membrane distillation performances.

Superhydrophobic polyvinylidene fluoride (PVDF) membrane is a promising material for membrane distillation. Existing approaches for preparing superhydrophobic PVDF membrane often involve separate manipulation of surface roughness and surface chemistry. Here we report a one-step approach to simultaneously manipulate both the surface roughness and surface chemistry of PVDF nanofibrous membranes for enhanced direct-contact membrane distillation (DCMD) performances. The manipulation was realized in a unique solvent-thermal treatment process, during which a treatment solution containing alcohols was involved. We demonstrate that by using different chain-length alcohols in the treatment solvent, surface roughness can be promoted by creating nanofin structures on the PVDF nanofibers using an alcohol which has moderate affinity with PVDF. Meanwhile, surface chemistry can be tuned by adjusting the fraction distribution of crystal phases (nonpolar α phase and polar ß phase) in the membrane using different alcohols. PVDF membranes with different surface wettabilities were used to evaluate the effects of surface roughness and surface energy on the DCMD performances. Combining both low surface energy and multi-scale surface roughness, pentanol-treated PVDF membrane achieved best anti-water property (water contact angle of 164.1° and sliding angle of 8.1°), and exhibited superior water flux and enhanced anti-wetting ability to low-surface-tension feed in the DCMD application.

Highly permeable and highly selective ultrathin film composite polyamide membranes reinforced by reactable polymer chains.

This study reports highly permeable ultrathin film composite (uTFC) membranes whose rejection layer was reinforced by polymer chains during the interfacial polymerization of trimesoyl chloride (TMC) and m-phenylenediamine (MPD) to achieve enhanced salt rejection. A rejection layer of approximately 20 nm was formed at an MPD concentration of 0.01 wt%. This reinforced membrane had a water permeability of about 16.7 L/(m2 h bar), while exhibiting an improved divalent salt (Na2SO4) to monovalent salt (NaCl) selectivity compared with the control TFC membrane without reinforcement (3.44 vs. 1.06). The role of the reactable polymer chains in interfacial polymerization was discussed as MPD adsorbent and reactant, according to the measurements by quartz crystal microbalance and X-ray photoelectron spectroscopy. This work provides a new pathway for the design and construction of uniform ultrathin layers as well as the preparation of high performance separation membranes.

Hydrophilic Silver Nanoparticles Induce Selective Nanochannels in Thin Film Nanocomposite Polyamide Membranes.

Thin-film nanocomposite (TFN) membranes have been widely studied over the past decade for their desalination applications. For some cases, the incorporation of nonporous hydrophilic nanofillers has been reported to greatly enhance membrane separation performance, yet the underlying mechanism is poorly understood. The current study systematically investigates TFN membranes incorporated with silver nanoparticles (AgNPs). For the first time, we reveal the formation of nanochannels of approximately 2.5 nm in size around the AgNPs, which can be attributed to the hydrolysis of trimesoyl chloride monomers and thus the termination of interfacial polymerization by the water layer around each hydrophilic nanoparticle. These nanochannels nearly tripled the membrane water permeability for the optimal membrane. In addition, this membrane showed increased rejection against NaCl, boron, and a set of small-molecular organic compounds (e.g., propylparaben, norfloxacin, and ofloxacin), thanks to its combined effects of improved size exclusion, enhanced Donnan exclusion, and suppressed hydrophobic interaction. Our work provides fundamental insights into the formation and transport mechanisms involved in solid-filler incorporated TFN membranes. Future studies should take advantage of this spontaneous nanochannel formation in the design of TFN to overcome the classical membrane permeability-selectivity trade-off.

Non-Polyamide Based Nanofiltration Membranes Using Green Metal-Organic Coordination Complexes: Implications for the Removal of Trace Organic Contaminants.

Polyamide-based thin film composite (TFC) membranes are generally optimized for salt rejection but not for the removal of trace organic contaminants (TrOCs). The insufficient rejection of TrOCs such as endocrine disrupting compounds (EDCs) by polyamide membranes can jeopardize product water safety in wastewater reclamation. In this study, we report a novel nonpolyamide membrane chemistry using green tannic acid-iron (TA-Fe) complexes to remove TrOCs. The nanofiltration membrane formed at a TA-Fe molar ratio of 1:3 (TA-Fe3) had a continuous thin rejection layer of 10-30 nm in thickness, together with a water permeability of 5.1 Lm2-h-1bar-1 and a Na2SO4 rejection of 89.7%. Meanwhile, this membrane presented significantly higher rejection of EDCs (up to 99.7%) than that of polyamide membranes (up to 81.8%). Quartz crystal microbalance results revealed that the sorption amount of a model EDC, benzylparbaen, by TA-Fe3 layer was nearly 2 orders of magnitude less than that by polyamide, leading to reduced transmission and higher rejection. Further analysis of membrane revealed a much greater water/EDC selectivity of the TA-Fe3 membrane compared to the polyamide membranes.

Tuning roughness features of thin film composite polyamide membranes for simultaneously enhanced permeability, selectivity and anti-fouling performance.

Thin film composite (TFC) polyamide membranes set the golden standard for reverse osmosis technology, but tuning their permeability and selectivity remains a major challenge because of the inherent permeability-selectivity trade-off. Creating nano-sized voids within the polyamide rejection layer can tune the membrane roughness and increase its effective filtration area to improve the water permeability. Here we prepare nano-foamed polyamide rejection layers by adding sodium bicarbonate into the aqueous solution of amine monomers. We show a systematic evolution of the roughness structure of polyamide membranes, with increasingly leaf-like and belt-like features appearing under enhanced nano-foaming conditions. These nano-foamed features can result in remarkable improvements in both water permeability and salt rejection and reduce membrane fouling propensity at the same time. Our study paves a new research direction for designing future generation of desalination membranes, which holds vast potential to reduce the cost and energy consumption of desalination while achieving improved product water quality.

Fast polydopamine coating on reverse osmosis membrane: Process investigation and membrane performance study.

We report a novel membrane surface modification method using a fast polydopamine coating (fPDAc) strategy. Specifically, NaIO4 was introduced in the coating process to accelerate the polydopamine deposition rate. Surface properties and separation performances of fPDAc-coated reverse osmosis membranes were characterized and compared to those obtained using the conventional slow polydopamine coating (sPDAc) strategy. Quartz crystal microbalance measurements showed greatly increased polydopamine deposition rate using the fPDAc method, resulting in a reduction of 97% coating time to reach an areal mass of 2000 ng/cm2. Both fPDAc and sPDAc enhanced the surface hydrophilicity and reduced the membrane surface charge. At relatively low areal mass deposition (<1000 ng/cm2), fPDAc-coated membranes showed improved NaCl rejection together with only mild loss of pure water flux. Nevertheless, this rejection enhancement effect was not noticeable when extensive polydopamine coating was applied due to the undesirable cake-enhanced concentration polarization effect. The extensive polydopamine coating was further accompanied with severe loss of membrane permeability, suggesting that shorter coating time (e.g., 4 min) is preferred using the fPDAc method. Our study provides a more rapid and effective membrane surface coating method compared to the conventional sPDAc method.

Tannic Acid/Fe3+ Nanoscaffold for Interfacial Polymerization: Toward Enhanced Nanofiltration Performance.

Conventional thin-film composite (TFC) membranes suffer from the trade-off relationship between permeability and selectivity, known as the "upper bound". In this work, we report a high performance thin-film composite membrane prepared on a tannic acid (TA)-Fe nanoscaffold (TFCn) to overcome such upper bound. Specifically, a TA-Fe nanoscaffold was first coated onto a polysulfone substrate, followed by performing an interfacial polymerization reaction between trimesoyl chloride (TMC) and piperazine (PIP). The TA-Fe nanoscaffold enhanced the uptake of amine monomers and provided a platform for their controlled release. The smaller surface pore size of the TA-Fe coated substrate further eliminated the intrusion of polyamide into the substrate pores. The resulting membrane TFCn showed a water permeability of 19.6 ± 0.5 L m2- h-1 bar-1, which was an order of magnitude higher than that of control TFC membrane (2.2 ± 0.3 L m-2 h-1 bar-1). The formation of a more order polyamide rejection layer also significantly enhanced salt rejection (e.g., NaCl, MgCl2, Na2SO4, and MgSO4) and divalent to monovalent ion selectivity (e.g., NaCl/MgSO4). Compared to conventional TFC nanofiltration membranes, the novel TFCn membrane successfully overcame the longstanding permeability and selectivity trade-off. The current work paves a new avenue for fabricating high performance TFC membranes.

A One-Step Rapid Assembly of Thin Film Coating Using Green Coordination Complexes for Enhanced Removal of Trace Organic Contaminants by Membranes.

We report a fast, simple, and green coating method using the coordination complex of tannic acid (TA) and ferric ion (Fe3+) to enhance the removal of trace organic contaminants (TrOCs) by polyamide membranes. The entire coating process can be completed in less than 2 min; quartz crystal microbalance characterization revealed that a TA-Fe thin film formed in merely 10-20 s. Coating this TA-Fe thin film on a commercial nanofiltration membrane (NF270) reduced its effective pore size from 0.44 to 0.40 nm. The TA-Fe-coated NF270 showed significantly increased rejection of both NaCl and trace organic contaminants. In comparison with the more-time-consuming polydopamine coating (e.g., 0.5 h), the TA-Fe coating presented greater resistance to TrOC permeation (i.e., lower permeability of TrOCs). The advantages of the fast coating process, greatly improved rejection performance, and use of green accessible materials make TA-Fe a highly promising coating material for large-scale applications.

A highly selective surface coating for enhanced membrane rejection of endocrine disrupting compounds: Mechanistic insights and implications.

We designed a highly selective surface coating to achieve enhanced rejection of endocrine disrupting compounds (EDCs) by nanofiltration membranes. A commercial NF90 membrane was first coated with polydopamine (PDA) followed by in situ immobilization of silver nanoparticles (AgNPs). This PDA/AgNPs coating greatly improved EDC rejection at the expense of slight water permeability loss (4-10%). This improvement in rejection can be attributed to a combination of enhanced size exclusion and suppressed hydrophobic interaction. A resistance-in-series analysis further reveals that the coating was highly permeable to water but highly resistant to EDCs, leading to an EDC selectivity that was an order of magnitude greater than those of the bare PDA coating and the base membrane NF90. The current study provides important insights into the design of highly selective coatings for effective retention of targeted trace organic contaminants.

Composition and properties of porous blend membranes containing tertiary amine based amphiphilic copolymers with different sequence structures.

Four tertiary amine based amphiphilic copolymers with similar composition but different sequence structures in terms of diblock (Poly(dimethylamino-2-ethyl methacrylate-b-methyl methacrylate) (P(MMA-b-DMAEMA))), triblock (P(DMAEMA-b-MMA-b-DMAEMA)), four-armed diblock (P(MMA-b-DMAEMA)4) and random (P(MMA-r-DMAEMA)) were synthesized and used for fabricating functional porous membranes by blending method. The retention ratios and surface enrichment ratios of the copolymers in blend membranes were determined by hydrogen nuclear magnetic resonance ((1)H-NMR) and X-ray photoelectron spectroscopy (XPS). The composition of the formed membranes was investigated and the durability was experimentally tested. The hydrophilicity of the membranes was evaluated by water contact angle measurement. The performance of membranes under different conditions including water fluxes at different pH and various ionic strength, the adsorption capabilities for Cr(VI) and negatively charged dye sunset yellow at different pH was studied. The results show that tertiary amine based amphiphilic copolymers with block and multi-armed sequence structures enable the blend membranes with higher copolymer retention ratios, more surface tertiary amine groups contents and better composition stability as well as more sensitive to the variation of pH, ionic strength, higher equilibrium anions, and negatively charged dyes uptakes.