Model Organic Foulants Research Articles

Probing molecular interaction mechanisms of organic fouling on polyamide membrane using a surface forces apparatus: Implication for wastewater treatment

Surface fouling is the dominant fouling mechanism of thin-film composite (TFC) membranes used in reverse osmosis (RO) technology. Understanding the complex interactions between foulant-membrane which drive the attachment and growth of foulants on membrane surface is of both fundamental and practical importance. This work aims to understand the molecular interaction mechanisms of organic fouling on RO-TFC membranes. A surface forces apparatus (SFA) was employed to directly measure the interaction forces and time-dependent adsorption behaviors between model organic foulants: humic acid (HA), bovine serum albumin (BSA), and lipopolysaccharides (LPS) and a polyamide (PA) thin film. PA thin film was prepared by interfacial condensation polymerization on mica substrates using m-phenylenediamine and 1,3,5-benzenetricarbonyltrichloride. The interaction forces between PA films and different foulant (HA, BSA, LPS) were directly measured under controlled solution chemistries in an asymmetric configuration (foulant-deposited PA films vs. PA films). The adsorption behaviors of these foulants on PA films were directly monitored in a symmetric configuration (PA films vs. PA films). These interactions were examined as a function of both contact time and solution chemistry (ionic strength). In asymmetrical configuration, both HA and BSA show repulsion with PA surface during approach and adhesion during separation, but LPS demonstrates repulsion only. In symmetrical configuration, all the foulants show adsorption on PA surface and the initial adsorption rate of foulant to PA surface follows the order of BSA>LPS>HA. The interaction mechanisms between PA films and foulants were discussed based on the interaction forces and interaction dynamics measurement.

Fouling mechanism of hydrophobic polytetrafluoroethylene (PTFE) membrane by differently charged organics during direct contact membrane distillation (DCMD) process: An especial interest in the feed properties

The growing attention to membrane distillation (MD) processes from various disciplines raises the demand for systematic research on MD membrane fouling. This study investigates the role of feed properties, such as feed compositions, charge properties, particle size, hydrophobicity/hydrophilcity, thermal stability and intermolecular interactions, in organic fouling of direct contact membrane distillation (DCMD). The differently charged lysozyme (LYS), sodium alginate (SA), and bovine serum albumin (BSA) were chosen as model organic foulants. The fouling data showed that the feed containing LYS and SA displayed a more severe flux decline compared to the BSA/SA solution, which was highly associated with the charge interaction. Additionally, the flux performance for the mixed foulants was partly affected by the proportion of protein (BSA or LYS) to polysaccharide (SA). It was found that the mixed feed containing less BSA caused a faster flux decline, whereas the feed containing higher amounts of LYS exhibited a more severe membrane fouling. Based on the membrane characterization analysis using FTIR, the BSA and SA showed significant conformational changes during the feed heating process, which largely aggravated the membrane fouling rate. Furthermore, the membrane fouling degree was proven to be distinctly affected by the sites where fouling occurred according to the SEM-EDX analysis. The results exhibited that SA was primarily deposited on the membrane surface, while the LYS largely penetrated into the pores, causing a more severe membrane fouling. Finally, two different fouling patterns including “egg-box model” and “multi-layer model” were suggested for the BSA/SA and LYS/SA feeds during the DCMD operation process, respectively.

Enhanced antifouling and antibacterial properties of poly (ether sulfone) membrane modified through blending with sulfonated poly (aryl ether sulfone) and copper nanoparticles

A series of novel blend ultrafiltration (UF) membranes have been successfully prepared from commercial poly (ether sulfone), lab-synthesized sulfonated poly (aryl ether sulfone) (SPAES, 1wt%) and copper nanoparticles (0∼0.4wt%) via immersion precipitation phase conversion. The micro-structure and separation performance of the membranes were characterized by field emission scanning electron microscopy (SEM) and cross-flow filtration experiments, respectively. Sodium alginate, bovine serum albumin and humic acid were chosen as model organic foulants to investigate the antifouling properties, while E. coil was used to evaluate the antibacterial property of the fabricated membranes. By the incorporation with SPAES and copper nanoparticles, the hydrophilicity, antifouling and antibacterial properties of the modified UF membranes have been profoundly improved. At a copper nanoparticles content of 0.4wt%, the PES/SPAES/nCu(0.4) membrane exhibited a high pure water flux of 193.0kg/m2h, reaching the smallest contact angle of 52°, highest flux recovery ratio of 79% and largest antibacterial rate of 78.9%. Furthermore, the stability of copper nanoparticles inside the membrane matrix was also considerably enhanced, the copper nanoparticles were less than 0.08mg/L in the effluent during the whole operation.

Effects of tannic acid on membrane fouling and membrane cleaning in forward osmosis.

The fouling behavior during forward osmosis (FO) was investigated. Tannic acid was used as a model organic foulant for natural organic matter analysis since the main characteristics are similar, and calcium ions were added at different concentrations to explore the anti-pollution capability of FO membranes. The initial permeate flux and calcium ions strength were varied in different operating conditions to describe membrane fouling with membrane cleaning methods. The observed flux decline in FO changed dramatically with the type of foulant and the type of draw solution used to provide the osmotic driving force. Calcium ions aggravated membrane fouling and decreased transmembrane flux. Membrane cleaning methods included physical and physicochemical approaches, and there was no obvious difference among the typical cleaning methods (i.e., membrane flushing with different types of cleaning fluids at various crossflow velocities and backwashing with varying osmotic driving forces) with respect to flux recovery. Ultrasonic cleaning damaged the membrane structure and decreased permeate flux, and reverse diffusion of salt from the draw solution to the feed side accelerated after cleaning.

Comparison of organic fouling resistance of thin-film composite membranes modified by hydrophilic silica nanoparticles and zwitterionic polymer brushes

We conducted a comparative study to investigate the efficacies of two different types of highly hydrophilic materials (i.e., silica nanoparticles (SiNPs) and zwitterionic polymers) for antifouling surface modification of polyamide thin-film composite (TFC) membranes. Dense layers of SiNPs and zwitterionic polymer brushes were grafted on the membrane surfaces via dip-coating with aminosilane-functionalized SiNPs (i.e., SiNP-TFC membrane) and surface-initiated atom-transfer radical-polymerization of sulfobetaine methacrylate (i.e., PSBMA-TFC membrane), respectively. With the same degree of enhancement of surface hydrophilicity and identical surface roughness, the PSBMA-TFC membrane exhibited significantly higher fouling resistance than the SiNP-TFC membrane in adsorption tests of proteins and bacteria as well as in forward osmosis (FO) dynamic fouling experiments using alginate as a model organic foulant. Chemical force microscopy measurements revealed that membrane-foulant electrostatic attraction aggravates organic fouling of the SiNP-TFC membrane to a certain degree, but the primary fouling mechanism is the complexation of organic foulants with carboxylic groups on the polyamide membrane surface. We attribute the lower fouling resistance of the SiNP-TFC membrane to the high density of surface carboxylic groups that may still be accessible to foulants as well as to membrane-foulant electrostatic interaction. On the contrary, the zwitterionic polymer brushes effectively shield the surface carboxylic groups and provide steric hindrance against foulant adsorption due to significant hydration of the zwitterionic brushes.

Organic fouling in surface modified reverse osmosis membranes: Filtration studies and subsequent morphological and compositional characterization

In this article, we report effect of surface coatings on organic fouling in reverse osmosis (RO) desalination membranes at the two operating pressure extremes of 20.7 and 55.2bar. The surface of commercial RO membranes was modified by depositing surface-enriched zwitterionic films in order to achieve enhanced organic fouling resistance. Antifouling performance of both the surface-modified and bare (uncoated) RO membranes was evaluated under cross-flow filtration conditions in the presence of sodium alginate (SA). Filtration studies of the model organic foulant solution showed that both reversible and irreversible flux declines were significantly lower and, as a result, considerably higher flux recovery was achieved after simple hydraulic flushing in the surface-modified membranes when compared to virgin RO membranes. The FE-SEM analysis revealed that foulant deposition on the surface of the modified membranes was patchy/irregular and porous in structure at both lower and higher pressures as opposed to dense and continuous foulant deposition with full coverage of bare membranes with SA at both low and high operating pressures. FTIR scans also qualitatively confirmed a higher amount of SA deposition and revealed that the foulant deposition is further enhanced at higher operating pressure of 55.2bar on the surface of bare membranes.

Fabrication and Assessment of ZnO Modified Polyethersulfone Membranes for Fouling Reduction of Bovine Serum Albumin

ZnO/PES composite membranes were fabricated by phase inversion method using DMAc as a solvent. The structure of ZnO was investigated using TEM, SEM, XRD, and TGA. TEM images of ZnO nanoparticles were well-defined, small, and spherically shaped with agglomerated nanoparticles particles of 50 nm. The SEM and XRD results were an indication that ZnO nanoparticles were present in the prepared ZnO/PES composites membranes. Contact angle measurements were used to investigate surface structures of the composite membranes. The amount of ZnO nanoparticles on PES membranes was varied to obtain the optimal performance of the composite membranes in terms of pure water flux, flux recovery, and fouling resistance using the protein bovine serum albumin (BSA) as a model organic foulant. The results showed that addition of ZnO to PES membranes improved the hydrophilicity, permeation, and fouling resistance properties of the membranes. Pure water flux increased from a low of 250 L/m2h for the neat membrane to a high of 410 L/m2h for the composite membranes. A high flux recovery of 80–94% was obtained for the composite membranes. The optimal performance of the composite membranes was obtained at 1.5 wt% of ZnO.

Mitigation of Biofilm Development on Thin-Film Composite Membranes Functionalized with Zwitterionic Polymers and Silver Nanoparticles.

We demonstrate the functionalization of thin-film composite membranes with zwitterionic polymers and silver nanoparticles (AgNPs) for combating biofouling. Combining hydrophilic zwitterionic polymer brushes and biocidal AgNPs endows the membrane with dual functionality: antiadhesion and bacterial inactivation. An atom transfer radical polymerization (ATRP) reaction is used to graft zwitterionic poly(sulfobetaine methacrylate) (PSBMA) brushes to the membrane surface, while AgNPs are synthesized in situ through chemical reduction of silver. Two different membrane architectures (Ag-PSBMA and PSBMA-Ag TFC) are developed according to the sequence AgNPs, and PSBMA brushes are grafted on the membrane surface. A static adhesion assay shows that both modified membranes significantly reduced the adsorption of proteins, which served as a model organic foulant. However, improved antimicrobial activity is observed for PSBMA-Ag TFC (i.e., AgNPs on top of the polymer brush) in comparison to the Ag-PSBMA TFC membrane (i.e., polymer brush on top of AgNPs), indicating that architecture of the antifouling layer is an important factor in the design of zwitterion-silver membranes. Confocal laser scanning microscopy (CLSM) imaging indicated that PSBMA-Ag TFC membranes effectively inhibit biofilm formation under dynamic cross-flow membrane biofouling tests. Finally, we demonstrate the regeneration of AgNPs on the membrane after depletion of silver from the surface of the PSBMA-Ag TFC membrane.

In situ visualization of organic fouling and cleaning mechanisms in reverse osmosis and forward osmosis

Fouling models rely on knowledge of foulant accumulation and removal mechanisms. In this study, a fouling visualization apparatus is developed to elucidate centimeter-scale mechanisms of organic fouling and cleaning in reverse osmosis (RO) and forward osmosis (FO). Alginate is used as a model organic foulant and dyed with methylene blue, which is shown not to affect fouling or cleaning, and to sufficiently highlight the gel for visualization at low salinity (up to 1% NaCl). When cleaning by increasing the cross-flow velocity, with or without reverse permeation, foulant peels off the membrane in discrete pieces in both RO and FO. Videos of cleaning show that foulant cake swelling and wrinkling can facilitate gel detachment and removal. Despite their effectiveness in slowing fouling, spacers can hinder removal of detached foulant pieces by obstructing their path. Finally, photographs point to a new mechanism of internal fouling in FO: vapor formation due to sub-atmospheric pressure within the membrane. Awareness of these mechanisms allows for better modeling of fouling and motivates optimization of swelling-inducing cleaning procedures.

Understanding the risk of scaling and fouling in hollow fiber forward osmosis membrane application

Abstract Fouling studies of forward osmosis (FO) were mostly conducted based on fouling evaluation principals applied to pressure membrane processes such as reverse osmosis (RO)/nanofiltration (NF)/microfiltration (MF)/ultrafiltration (UF). For RO/NF/MF/UF processes, the single flux driving force (hydraulic pressure) remains constant, thus the fouling effect is easily evaluated by comparing flux data with the baseline. Whilst, the scenario of fouling effects for FO process is entirely different from RO/NF/MF/UF processes. Continuously changing driving force (osmotic pressure difference), the changes in concentration polarization associated with the varying draw solution/feed solution concentration and the fouling layer effects collectively influence the FO flux. Thus, usual comparison of the FO flux outcome with the baseline results cannot exactly indicate the real affect of membrane fouling, rather presents a misleading cumulative effect. This study compares the existing FO fouling technique with an alternate fouling evaluation approach using two FO set-ups. Scaling and fouling risk for hollow fiber FO was separately investigated using synthetic water samples and model organic foulants as alginate, humic acid and bovine serum albumin. Results indicated that FO flux declines up to 5% and 49% in active layer-feed solution and active layer-draw solution orientations respectively.

The synergistic effect of organic foulants and their fouling behavior on the nanofiltration separation to multivalent ions

This work aimed to determine the effect of organic foulants and fouling behavior on separation of multi-ions for nanofiltration (NF) membrane. Three model organic foulants (bovine serum albumin, lysozyme, and humic acid) were selected and studied in depth. The rejections of mono- and di-anions by virgin membrane varied with different organic foulants because of foulant-enhanced co-ion competition. Subsequent multi-ions separations by fouled membranes were different due to the zeta potential and structure of the fouling cake. In contrast to the single protein system, Cl− and SO42- rejection was reduced by HA fouled membrane. However, with added proteins in the HA solution, mixed systems experienced decreasing Cl− rejection and increasing SO42- rejection. In addition, solution chemistry (solution pH, ionic strength, and Ca2+) had marked effect on the cake layer composition, likely due to the changing interaction between foulant and foulant, as well as between foulant and NF membrane. The suitable foulant cake structure could result enhanced in multi-ions separation. The synergistic mechanisms of organic foulants and cake were analyzed by calculated cake hydraulic resistance and zeta potential of fouled membranes.

A synergetic analysis method for antifouling behavior investigation on PES ultrafiltration membrane with self-assembled TiO2 nanoparticles

Fouling of ultrafiltration (UF) membranes is a major impediment for their use in drinking water production. Mixed matrix membranes (MMMs) may have great opportunities in dealing with this challenge due to their hierarchical structures and multiple functionalities. In this study, a synergetic analysis method based on intermolecular adhesion force measurement and fouling process simulation was applied to investigate the fouling mechanism of polyethersulfone (PES) UF membranes containing in situ self-assembled TiO2 nanoparticles (NPs). The fouling resistance behavior and antifouling mechanism of the newly developed composite membranes were investigated with sodium alginate (SA), bovine serum albumin (BSA) and humic acid (HA) as model organic foulants. An improved antifouling effect was conspicuously observed for the composite membranes, expressed by a lower flux decline and significantly better cleaning efficiency. A strong correlation between the self-assembled structure of TiO2 NPs and the antifouling behavior of the composite membrane was observed. A lower magnitude and a narrower distribution of adhesion forces for the composite membrane suggest the effective suppression of foulants adsorption on the clean or fouled membrane. The simulation analysis indicates that the main fouling mechanism was standard blocking and cake filtration, further confirming the superiority of the NPs self-assembled structure in mitigating membrane fouling. This dual analysis method may provide a promising technological support for the application of modified UF membranes with self-assembled NPs in drinking water production.

Forward osmosis filtration for removal of organic foulants: Effects of combined tannic and alginic acids

The filtration performance of combined organic foulants by forward osmosis (FO) in active-layer-facing-the-draw-solution (AL-facing-DS) orientation was investigated systematically. Tannic acid and alginate were used as model organic foulants for polysaccharides and humic dissolved organic matters, respectively. The FO could reject combined and single tannic acid and alginate foulants effectively. The more severe fouling flux decline, accompanied with lower combined foulants' retention, was observed with increasing proportions of tannic acid in the combined foulants-containing feed, which was ascribed mainly to the more severe fouling resulting from tannic acid adsorption within the porous support layer of the FO membrane compared to minor alginate deposition on the membrane surface. It was found that the higher the initial flux level and cross flow velocity, the faster the flux decline with lower mixed foulants retention. It was also revealed that the calcium ions in a basic solution enhanced the combined fouling flux reduction and combined foulants retention. As the major constituent of the combined fouling layer, the adsorption of tannic acid might play a more significant role in the mixed fouling of the FO membrane, which was probably influenced by permeation drag caused by water flux and chemical interactions induced by feed solution pH and calcium ion concentration.

Organic Fouling of Graphene Oxide Membranes and Its Implications for Membrane Fouling Control in Engineered Osmosis.

This study provides experimental evidence to mechanistically understand some contradicting effects of the characteristic properties of graphene oxide (GO), such as the high hydrophilicity, negative charge, strong adsorption capability, and large surface area, on the antifouling properties of GO membranes. Furthermore, this study demonstrates the effectiveness of forming a dense GO barrier layer on the back (i.e., porous) side of an asymmetric membrane for fouling control in pressure-retarded osmosis (PRO), an emerging engineered osmosis process whose advancement has been much hindered due to the severe irreversible fouling that occurs as foulants accumulate inside the porous membrane support. In the membrane fouling experiments, protein and alginate were used as model organic foulants. When operated in forward osmosis mode, the GO membrane exhibited fouling performance comparable with that of a polyamide (PA) membrane. Analysis of the membrane adsorption capacity showed that, likely due to the presence of hydrophobic regions in the GO basal plane, the GO membrane has an affinity toward organic foulants 4 to 5 times higher than the PA membrane. Such a high adsorption capacity along with a large surface area, however, did not noticeably aggravate the fouling problem. Our explanation for this phenomenon is that organic foulants are adsorbed mainly on the basal plane of GO nanosheets, and water enters the GO membrane primarily around the oxidized edges of GO, making foulant adsorption not create much hindrance to water flux. When operated in PRO mode, the GO membrane exhibited much better antifouling performance than the PA membrane. This is because unlike the PA membrane for which foulants can be easily trapped inside the porous support and hence cause severe irreversible fouling, the GO membrane allows the foulants to accumulate primarily on its surface due to the sealing effect of the GO layer assembled on the porous side of the asymmetric membrane support. Results from the physical cleaning experiments further showed that the water flux of GO membranes operated in PRO mode can be sufficiently restored toward its initial prefouling level.

Inherent porous structure modified by titanium dioxide nanoparticle incorporation and effect on the fouling behavior of hybrid poly(vinylidene fluoride) membranes

ABSTRACTThe incorporation of nanoparticles (NPs) into a casting solution is a widely used practice for controlling the membrane fouling tendency, but the specific role of NPs in fouling control from an internal porous structure optimization has seldom been investigated. In this study, we evaluated the specific role of titanium dioxide (TiO2)–NPs (Degussa P25) in mitigating membrane organic fouling. We prepared the membranes by tailoring the concentrations of the NPs well; this resulted in an optimized membrane microstructure consisting of fingerlike voids (beneath the skin layer of the membrane) and spongy voids (adjacent to the fingerlike voids). The NP incorporation induced the formation of spongy voids beneath the skin layer, and the increase in the NP concentration increased the formation of spongy voids. Moreover, surface images obtained by scanning electron microscopy, X‐ray photoelectron spectroscopy results, and contact angles confirmed that TiO2–NPs were almost absent on the skin layer. Antifouling experiments were performed with a model organic foulant in two flow orientations [fingerlike voids facing the retentate (FVR) and spongy voids facing the retentate (SVR)]. The results show that the membrane fluxes in FVR decreased more than those in SVR. The membrane with 1.5 wt % TiO2 operated in SVR exhibited the lowest flux decline; this suggested that spongy voids with TiO2 exposure could mitigate fouling to a greater extent. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43265.

Investigation of combined fouling behavior in nano-filtration process under various feed conditions

ABSTRACTDespite the great advance in nano-filtration (NF) process development in various applications, its performance in water treatment is still impeded by the undesired fouling phenomenon, which is not yet fully understood nowadays. In this study, a comprehensive investigation on the fouling behavior, more specifically the combined fouling behavior with the presence of more than one type of foulant was carried out under various solution chemistries and feed hydraulic pressures. The interaction between the model organic foulant (alginate) and inorganic foulant (silica colloid) was systematically studied with nano-filtration membranes, with a more severe fouling observed in the combined fouling than individual foulants. However, the results also revealed that the commonly observed synergistic effect of combined fouling in the forward osmosis process was not present in the nano-filtration process. In addition, the solution chemistries (pH and calcium ions) and feed hydraulic pressure were also found to have certain influence on the combined fouling, especially the feed hydraulic pressure which exhibited a more pronounced impact on the flux decline than the other factors, thus in turn, affecting more on the reversibility of the membrane fouling.

Reverse osmosis membranes surface-modified using an initiated chemical vapor deposition technique show resistance to alginate fouling under cross-flow conditions: Filtration & subsequent characterization

The surface of commercial reverse osmosis (RO) membranes was modified by the deposition of 2-hydroxyethyl methacrylate-co-perfluorodecyl acrylate (HEMA-co-PFDA) copolymer films using an initiated chemical vapor deposition (iCVD) technique. Antifouling characteristics of the modified and unmodified membranes were evaluated under cross-flow permeation conditions using sodium alginate as a model organic foulant. The permeate flux decline was lower in the surface-modified membranes as compared to the virgin ones while salt rejection remained almost unaltered in both virgin and coated membranes. The presence of the HEMA-co-PFDA copolymer on the fouled membrane surface is confirmed by simultaneous analyses with Attenuated Total Reflectance–Fourier Transform Infra-Red (ATR-FTIR) and X-ray Photoelectron Spectroscopy. Field Emission Scanning Electron Microscopy (FESEM) images showed a dense and continuous foulant layer on the virgin samples as opposed to a porous and discontinuous one for the coated membranes. The water contact angle values for the coated membranes registered a decrease indicating the more hydrophilic nature of the adsorbed alginate. To conclude, although fouling appears inevitable, it is considerably slowed down by this surface modification strategy.

Role of various physical and chemical techniques for hollow fibre forward osmosis membrane cleaning

Fouling is an inevitable phenomenon with most of the water treatment systems. Similar to RO, NF and other membrane-based systems, fouling also seriously affects the performance of low-cost forward-osmosis (FO) systems and disturbs the overall efficiency of these systems, and various cleaning practices have been evaluated to restore their designed performances. This study evaluates the performance of various physical and chemical cleaning techniques for hollow fibre forward-osmosis (HFFO) membrane. HFFO membrane was subjected to various fouling conditions using different brackish groundwater qualities and model organic foulants such as alginate, humic acid and bovine serum albumin. Results indicated that physical cleaning affects differently the flux restoration according to the type of foulants (i.e. inorganic or organic) and the crossflow rates play an important role in membrane cleaning in both membrane orientation. The higher cross flow Re values at any particular area seem important for the cleaning. With hydraulic flushing, the flux performances of HFFO were recovered fully when operated in AL-FS orientation, as high shear force helps to detach all scaling layers from the surface; however, the lower shear force did not fully restore the flux for the FS membrane in AL-DS orientation. Chemical cleaning was planned for the fouled HFFO membrane, and HCl and NaOH were used in various combination sequences. It was found that HCl did not clean the membrane used for AL-DS orientation for combined fouling. HCl cleaning (at pH 2) was found to be more effective for removing inorganic scale, whereas NaOH cleaning (at pH 11) for a similar period successfully restored the flux for all the membranes used for FS with inorganic and/or organic foulants. ethylenediamine tetra acetic acid (EDTA) was also evaluated for its cleaning performances and it was found that compared to NaOH, EDTA cleaning (1mM concentration at pH 11) showed superior results in terms of membrane cleaning, as it helped to successfully restore the membrane flux in a very short time.

Role of pressure in organic fouling in forward osmosis and reverse osmosis

Fundamental understanding of membrane fouling in osmosis-driven membrane processes is important for further deployment of this emerging technology in desalination and wastewater reuse. In this study, we investigated the role of pressure in organic fouling and reversibility in forward osmosis (FO) and reverse osmosis (RO) using alginate as a model organic foulant. Varying contributions of pressure (i.e., osmotic versus hydraulic) to the overall driving force were realized in forward osmosis (FO), pressure-assisted FO (PFO), and reverse osmosis (RO) experiments, while the same total driving force for water permeation was applied. Confocal laser scanning microscopy was used to examine alginate fouling layer structure in the hydrated state, which informed two key parameters: fouling layer thickness and foulant volume. We observed that the resulting fouling layer became increasingly more compact in the order of FO, PFO, and RO experiments. Fouling layer reversibility followed the same trend, with the highest and lowest reversibility observed for the FO and RO fouling experiments, respectively. Possible mechanisms for fouling layer compaction in RO were discussed, including permeate drag force and foulant compressibility, as opposed to FO where only permeate drag force applies. Our findings suggest that pressure mechanistically alters the membrane fouling layer structure and fouling reversibility, leading to higher fouling reversibility in FO, where the driving force is osmotic pressure, than RO, where the driving force is hydraulic pressure.

Engineered crumpled graphene oxide nanocomposite membrane assemblies for advanced water treatment processes.

In this work, we describe multifunctional, crumpled graphene oxide (CGO) porous nanocomposites that are assembled as advanced, reactive water treatment membranes. Crumpled 3D graphene oxide based materials fundamentally differ from 2D flat graphene oxide analogues in that they are highly aggregation and compression-resistant (i.e., π-π stacking resistant) and allow for the incorporation (wrapping) of other, multifunctional particles inside the 3D, composite structure. Here, assemblies of nanoscale, monomeric CGO with encapsulated (as a quasi core-shell structure) TiO2 (GOTI) and Ag (GOAg) nanoparticles, not only allow high water flux via vertically tortuous nanochannels (achieving water flux of 246 ± 11 L/(m(2)·h·bar) with 5.4 μm thick assembly, 7.4 g/m(2)), outperforming comparable commercial ultrafiltration membranes, but also demonstrate excellent separation efficiencies for model organic and biological foulants. Further, multifunctionality is demonstrated through the in situ photocatalytic degradation of methyl orange (MO), as a model organic, under fast flow conditions (tres < 0.1 s); while superior antimicrobial properties, evaluated with GOAg, are observed for both biofilm (contact) and suspended growth scenarios (>3 log effective removal, Escherichia coli). This is the first demonstration of 3D, crumpled graphene oxide based nanocomposite structures applied specifically as (re)active membrane assemblies and highlights the material's platform potential for a truly tailored approach for next generation water treatment and separation technologies.