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Severe acute respiratory syndrome coronavirus 2's (SARS-CoV-2) rapid global spread has posed a significant threat to human health, and similar outbreaks could occur in the future. Developing effective virus inactivation technologies is critical to preventing and overcoming pandemics. The infection of SARS-CoV-2 depends on the binding of the spike glycoprotein (S) receptor binding domain (RBD) to the host cellular surface receptor angiotensin-converting enzyme 2 (ACE2). If this interaction is disrupted, SARS-CoV-2 infection could be inhibited. Magnetic nanoparticle (MNP) dispersions exposed to an alternating magnetic field (AMF) possess the unique ability for magnetically mediated energy delivery (MagMED); this localized energy delivery and associated mechanical, chemical, and thermal effects are a possible technique for inactivating viruses. This study investigates the MNPs' effect on vesicular stomatitis virus pseudoparticles containing the SARS-CoV-2 S protein when exposed to AMF or a water bath (WB) with varying target steady-state temperatures (45, 50, and 55 °C) for different exposure times (5, 15, and 30 min). In comparison to WB exposures at the same temperatures, AMF exposures resulted in significantly greater inactivation in multiple cases. This is likely due to AMF-induced localized heating and rotation of MNPs. In brief, our findings demonstrate a potential strategy for combating the SARS-CoV-2 pandemic or future ones.

The role of steric hindrance and charge interactions in governing ionic transport through reduced graphene oxide (rGO) and commercial (DOW-Filmtec NF270) membranes was elucidated by a comprehensive study of experimental and established mathematical analysis based on Nernst-Planck equation. A charge-dominated salt exclusion mechanism was observed for the rGO membranes, which exhibited retention from low (7%) to moderate (70%) extent depending on the nature of ions (5 mM). Swelling of GO (1.2 nm interlayer distance) in water beyond the hydrated diameter of ions was attributed as a primary cause for lowering steric hindrance effects. The influence of parameters affecting charge interactions, such as pH and ionic strength, on the extent of salt rejection was modelled. The potential impact of the membrane's charge density, GO loading and interlayer spacing on salt retention was quantified by performing sensitivity analyses. For a high TDS produced water sample, the rGO membranes partially retained divalent cations (Ca:13%) and exhibited high dissolved oil rejection. The membranes were found to be suitable for the treatment of high TDS water with the goal of selectively removing organic impurities, and thus minimizing the impact of osmotic pressure effect. Performance of the membranes was also investigated for retention of water remediation related organic anions, using perfluoro octanoic (PFOA) acid as a model compound. rGO membranes exhibited a charge-dominated exclusion mechanism for retention (90%) of PFOA (1 ppm).

Challenges associated with water separation technologies for per- and polyfluoroalkyl substances (PFASs) require efficient and sustainable processes supported by a proper understanding of the separation mechanisms. The solute rejections by nanofiltration (NF) at pH values near the membrane isoelectric point were compared to the size- and mass-transfer-dependent modeled rejection rates of these compounds in an ionized state. We find that the low pK(a) value of perfluorooctanoic acid (PFOA) relates to enhanced solute exclusions by minimizing the presence and partitioning of the protonated organic compound into the membrane domain. The effects of Donnan exclusion are moderate, and co-ion transport also contributes to the PFAS rejection rates. An additional support barrier with thermo-responsive (quantified by water permeance variation) adsorption/desorption properties allows for enhanced separations of PFAS. This was possible by successfully synthesizing an NF layer on top of a poly-N-isopropylacrylamide (PNIPAm) pore-functionalized microfiltration support structure. The support layer adsorbs organics (178 mg PFOA adsorbed/m(2) membrane at an equilibrium concentration of 70 mg/L), and the simultaneous exclusion from the NF layer allows separations of PFOA and the smaller sized heptafluorobutyric acid from solutions containing 70 μg/L of these compounds at a high water flux of 100 L/m(2)-h at 7 bar.

Metallic thin-film composite membranes are produced by sputtering metal films onto commercial polymer membranes. The separations capability of the membrane substrate is enhanced with the addition of a 10 nm Ta film. The addition of a tantalum layer decreases the molecular weight cutoff of the membrane from 70 kDa dextran (19 nm) to below 5 kDa (6 nm). Water flux drops from 168 LMH/bar (LMH: liters/meters2/hour) (polymer support) to 8.8 LMH/bar (Ta composite). A nanoporous layer is also added to the surface through Mg/Pd film deposition and dealloying. The resulting nanoporous Pd is a promising catalyst with a ligament size of 4.1 ± 0.9 nm. The composite membrane's ability to treat water contaminated with chlorinated organic compounds (COCs) is determined. When pressurized with hydrogen gas, the nanoporous Pd composite removes over 70% of PCB-1, a model COC, with one pass. These nanostructured films can be incorporated onto membrane supports enabling diverse reactions and separations.

This study demonstrates a three-step process consisting of primary pre-filtration followed by ultrafiltration (UF) and adsorption with thiol-functionalized microfiltration membranes (thiol membranes) to effectively remove mercury sulfide nanoparticles (HgS NPs) and dissolved mercury (Hg2+) from wastewater. Thiol membranes were synthesized by incorporating either cysteine (Cys) or cysteamine (CysM) precursors onto polyacrylic acid (PAA)-functionalized polyvinylidene fluoride membranes. Carbodiimide chemistry was used to cross-link thiol (−SH) groups on membranes for metal adsorption. The thiol membranes and intermediates of the synthesis were tested for permeability and long-term mercury removal using synthetic waters and industrial wastewater spiked with HgS NPs and a Hg2+ salt. Results show that treatment of the spiked wastewater with a UF membrane removed HgS NPs to below the method detection level (20 h) was approximately 97%. Addition of Ca2+ cations reduced the adsorption efficiencies to 82% for the CysM membrane and to 40% for the Cys membrane. The inferior performance of Cys membranes may be explained by the presence of a carboxyl (−COOH) functional group in Cys, which may interfere in the adsorption process in the presence of multiple cations because of multication absorption. CysM membranes may therefore be more effective for treatment of wastewater than Cys membranes. Focused ion beam characterization of a CysM membrane cross section demonstrates that the adsorption of heavy metals is not limited to the membrane surface but takes place across the entire pore length. Experimental results for adsorptions of selected heavy metals on thiol membranes over a wide range of operating conditions could be predicted with modeling. These results show promising potential industrial applications of thiol-functionalized membranes.

Perfluoroalkyl compounds of various molecular weights have emerged as a class of persistent contaminants with profound negative impact on human health and the environment. The selectivity and permeance of Graphene Oxide (GO) and amine surface functionalised GO nanofiltration membranes were assessed for the removal of perfluorooctanoic acid (PFOA ∼400 Da) in concentration ranges relevant to availability in wastewater. GO nanofiltration membranes demonstrated a reasonable efficiency of 74.3% at 50 ppm of PFOA and a water permeance of 10 ± 2.1 L m−2 h−1 bar−1. By functionalising the top surface with polyethyleneimine (PEI), the GO membrane underwent reduction and cross-linking reactions. The modified membranes demonstrated improved mechanical stability and an enhanced retention of 96.5% at 50 ppm PFOA and a permeance of 15.9 ± 1.3 L m−2 h−1 bar−1. The electron rich PEI deoxygenates GO leading to a smaller interlayer spacing, but also increases the surface hydrophilicity—the combination of both these properties leads to increased PFOA retention by steric hindrance and enhanced water permeation. As steric hindrance effects were the dominant mechanism of retention, the GO-PEI membranes operated more effectively (retention >90%) in a much wider range of concentrations (100 ppb to 100 ppm), compared to the GO membrane. Our research demonstrates that strategic surface-modification techniques can tailor the effectiveness of GO-based loose nanofiltration membranes for the retention of emerging contaminants while maintaining lower osmotic pressure effects through salt retention minimisation.

A biological photoinduced fermentation process provides an alternative to traditional hydrogen productions. In this study, biohydrogen production was investigated at near IR region coupled to a near-field enhancement by silica-core gold-shell nanoparticles (NPs) over a range of acetate concentrations (5–40 mM) and light intensities (11–160 W/m(2)). The kinetic data were modeled using modified Monod equations containing light intensity effects. The yields of H(2) and CO(2) produced per acetate were determined as 2.31 mol-H(2)/mol-Ac and 0.83 mol-CO(2)/mol-Ac and increased to 4.38 mmol-H(2)/mmol-Ma and 2.62 mmol-CO(2)/mmol-Ma when malate was used. Maximum increases in H(2) and CO(2) productions by 115% and 113% were observed by adding NPs without affecting the bacterial growth rates (6.1–8.2 mg-DCM/L/hour) while the highest hydrogen production rate was determined as 0.81 mmol/L/hour. Model simulations showed that the energy conversion efficiency increased with NPs concentration but decreased with the intensity. Complete hydrogenation application was demonstrated with toxic 2-chlorobiphenyl using Pd catalysts.

Reduction of airborne viral particles in enclosed spaces is critical in controlling pandemics. Three different hollow fiber membrane (HFM) modules were investigated for viral aerosol separation in enclosed spaces. Pore structures were characterized by scanning electron microscopy, and air transport properties were measured. Particle removal efficiency was characterized using aerosols generated by a collision atomizer from a defined mixture of synthetic nanoparticles including SARS-CoV-2 mimics (protein-coated 100 nm polystyrene). HFM1 (polyvinylidene fluoride, ∼50–1300 nm pores) demonstrated 96.5–100% efficiency for aerosols in the size range of 0.3–3 μm at a flow rate of 18.6 ± 0.3 SLPM (∼1650 LMH), whereas HFM2 (polypropylene, ∼40 nm pores) and HFM3 (hydrophilized polyether sulfone, ∼140–750 nm pores) demonstrated 99.65–100% and 98.8–100% efficiency at flow rates of 19.7 ± 0.3 SLPM (∼820 LMH) and 19.4 ± 0.2 SLPM (∼4455 LMH), respectively. Additionally, lasting filtration with minimal fouling was demonstrated using ambient aerosols over 2 days. Finally, each module was evaluated with pseudovirus (vesicular stomatitis virus) aerosol, demonstrating 99.3% (HFM1), >99.8% (HFM2), and >99.8% (HFM3) reduction in active pseudovirus titer as a direct measure of viral particle removal. These results quantified the aerosol separation efficiency of HFMs and highlight the need for further development of this technology to aid the fight against airborne viruses and particulate matter concerning human health.

This study investigates the effect of palladium (Pd) form on the electrochemical degradation of chlorobenzene in groundwater by palladium-catalyzed electro-Fenton (EF) reaction. In batch and flow-through column reactors, EF was initiated via in-situ electrochemical formation of hydrogen peroxide (H(2)O(2)) supported by palladium on alumina powder or by palladized polyacrylic acid (PAA) in a polyvinylidene fluoride (PVDF) membrane (Pd-PVDF/PAA). In a mixed batch reactor containing10 mg L(−1) Fe(2+), 2 g L(−1) of catalyst in powder form (1% Pd, 20 mg L(−1) of Pd) and an initial pH of 3, chlorobenzene was degraded under 120 mA current following a first-order decay rate showing 96% removal within 60 min. Under the same conditions, a rotating Pd-PVDF/PAA disk produced 88% of chlorobenzene degradation. In the column experiment with automatic pH adjustment, 71% of chlorobenzene was removed within 120 min with 10 mg L(−1) Fe(2+), and 2 g L(−1) catalyst in pellet form (0.5% Pd, 10 mg L(−1) of Pd) under 60 mA. The EF reaction can be achieved under flow, without external pH adjustment and H(2)O(2) addition, and can be applied for in-situ groundwater treatment. Furthermore, the rotating PVDF-PAA membrane with immobilized Pd-catalyst showed an effective and low maintenance option for employing Pd catalyst for water treatment.

The simultaneous elimination of organic waste and the production of clean fuels will have an immense impact on both the society and the industrial manufacturing sector. The enhanced understanding of the interface between nanoparticles and photo-responsive bacteria will further advance the knowledge of their interactions with biological systems. Although literature shows the production of gases by photobacteria, herein, we demonstrated the integration of photonics, biology, and nanostructured plasmonic materials for hydrogen production with a lower greenhouse CO2 gas content at quantified light energy intensity and wavelength. Phototrophic purple non-sulfur bacteria were able to generate hydrogen as a byproduct of nitrogen fixation using the energy absorbed from visible and near-IR (NIR) light. This type of biological hydrogen production has suffered from low efficiency of converting light energy into hydrogen in part due to light sources that do not exploit the organisms' capacity for NIR absorption. We used NIR light sources and optically resonant gold–silica core–shell nanoparticles to increase the light utilization of the bacteria to convert waste organic acids such as acetic and maleic acids to hydrogen. The batch growth studies for the small cultures (40 mL) of Rhodopseudomonas palustris demonstrated >2.5-fold increase in hydrogen production when grown under an NIR source (167 ± 18 μmol H2) compared to that for a broad-band light source (60 ± 6 μmol H2) at equal light intensity (130 W m−2). The addition of the mPEG-coated optically resonant gold–silica core–shell nanoparticles in the solution further improved the hydrogen production from 167 ± 18 to 398 ± 108 μmol H2 at 130 W m−2. The average hydrogen production rate with the nanoparticles was 127 ± 35 μmol L−1 h−1 at 130 W m−2.

Emerging perfluoroalkyl and polyfluoroalkyl substances contaminate waters at trace concentrations, thus rapid and selective adsorbents are pivotal to mitigate the consequent energy-intensive and time-consuming issues in remediation. In this study, coal combustion residuals-fly ash was modified (FA-SCA) to overcome the universal trade-off between high adsorption capacity and fast kinetics. FA-SCA presented rapid adsorption (teq = 2 min) of PFOX (perfluorooctanoic acid and perfluorooctanesulfonic acid, collectively), where the dynamic adsorption capacity (qdyn = qm/teq) was 2–3 orders of magnitude higher than that of benchmark activated carbons and anion-exchange resins. Investigated by advanced characterization and kinetic models, the fast kinetics and superior qdyn are attributed to (1) elevated external diffusion driven by the submicron particle size; (2) enhanced intraparticle diffusion caused by the developed mesoporous structure (Vmeso/Vmicro = 8.1); (3) numerous quaternary ammonium anion-exchange sites (840 µmol/g), and (4) appropriate adsorption affinity (0.031 L/µmol for PFOS, and 0.023 L/µmol for PFOA). Since the adsorption was proven to be a synergistic process of electrostatic and hydrophobic interactions, effective adsorption ([PFOX]ini = 1.21 µM, concentration levels of highly-contaminant-sites) was obtained at conventional natural water chemistries. High selectivity (>85.4% removal) was also achieved with organic/inorganic competitors, especially compounds with partly similar molecular structures to PFOX. In addition, >90% PFOX was removed consistently during five cycles in mild regeneration conditions (pH 12 and 50 °C). Overall, FA-SCA showed no leaching issues of toxic metals and exhibits great potential in both single-adsorption processes and treatment train systems.

Pore functionalized membranes with appropriate ion exchange/chelate groups allow toxic metal sorption under convective flow conditions. This study explores the sorption capacity of ionic mercury in a polyvinylidene fluoride-poly(acrylic acid) (PVDFs-PAA) functionalized membrane immobilized with cysteamine (MEA). Two methods of MEA immobilization to the PVDF-PAA membrane have been assessed: (i) ion exchange (IE) and (ii) carbodiimide cross-linker chemistry using 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS), known as EDC/NHS coupling. The ion exchange method demonstrates that cysteamine (MEA) can be immobilized effectively on PVDF-PAA membranes without covalent attachment. The effectiveness of the MEA immobilized membranes to remove ionic mercury from the water was evaluated by passing a dissolved mercury(II) nitrate solution through the membranes. The sorption capacity of mercury for MEA immobilized membrane prepared by the IE method is 1015 mg/g PAA. On the other hand, the sorption capacity of mercury for MEA immobilized membrane prepared by EDC/NHS chemistry is 2446 mg/g PAA, indicating that membrane functionalization by EDC/NHS coupling enhanced mercury sorption 2.4 times compared to the IE method. The efficiencies of Hg removal are 94.1 ± 1.1 and 99.1 ± 0.1% for the MEA immobilized membranes prepared by IE and EDC/NHS coupling methods, respectively. These results show potential applications of MEA immobilized PVDF-PAA membranes for industrial wastewater treatment specifically from energy and mining industries to remove mercury and other toxic metals.

In this study a systematic comparison in morphology, long-term degradation, regeneration and reuse were conducted between palladized and sulfidized nanoscale zero-valent iron (Pd-Fe and S-Fe). Pd-Fe and S-Fe were prepared, after the synthesis of precursor Fe(0) nanoparticles (spherical, ~35 nm radius) for carbon tetrachloride (CTC) treatment. With HAADF-TEM-EDS characterization, dispersive Pd islets were found on the Fe core of Pd-Fe. However, the Fe core was covered by the FeS(x) shell of S-Fe (FeS/FeS(2) = 0.47). With an excessive Pd dose (10 mol%), the Pd-Fe were dramatically deformed to dendritic structures which significantly decreased reactivity. For CTC degradation, Pd-Fe (0.3 atomic% Pd) increased the degradation rate by 20-fold (k(sa)= 0.580 Lm(−2)min(−1)) while S-Fe presented a greater life time. The major intermediate chloroform (CF) was further degraded and less than 5% CF was observed after 24 h using Pd-Fe or S-Fe while above 50% CF remained using Fe. During aging, the Fe core was converted to FeOOH and Fe(3)O(4)/γ-Fe(2)O(3). The restoration of Fe(0) was achieved using NaBH(4), which regenerated Fe and Pd-Fe. However, the formed FeS(x) shell on S-Fe was disappeared. The results suggest that S-Fe extends longevity of Fe, but the loss of FeS(x) after aging makes S-Fe eventually perform like Fe in terms of CTC degradation.

This study explores the integration of separation performance of rGO membrane with heterogeneous oxidation reactions for remediation of organic contaminants from water. Herein, an approach was introduced based on layer-by-layer assembly for functionalizing rGO membranes with polyacrylic acid and then by in situ synthesis of Fe based reactive nanoparticles. TEM characterization of the cross-section lamella of the membranes showed a high density of nanoparticles (12% Fe) in the functionalized domain, signifying the importance of polyacrylic acid for in situ synthesis of nanoparticles. The membranes exhibited a pure water permeability of 1.9 LMH bar(−1). The membranes had low to moderate salt retention, and more than 90% neutral red retention (organic probe molecule, size: 1.2 nm). The membranes also exhibited high retention of humic acids (80%), preventing these organics from entering the reactive domain, and thus potentially reducing the formation of undesired by-products. A persulfate mediated oxidative pathway was employed to demonstrate the reactive removal of organic contaminants. The membranes achieved >95% conversion by convectively passing 2 mM persulfate feed at a transmembrane pressure of 0.4 bar. Successful degradation of TCE (up to 61%) was achieved in a single pass by convective flowing of the feed solution through the membrane, generating up to 80% of the theoretical maximum chloride as one of the byproducts. Elevated temperatures significantly enhanced persulfate mediated TCE oxidation extent from 24% at 23 oC to 54% at 40 o C under batch operating conditions.

Perfluoroalkyl and polyfluoroalkyl substances (PFAS) are emerging contaminants in water and soil. Electrospun membranes with open structure could treat PFAS in a gravity-driven mode with ultralow pressure needs. The electrospun ultrathin fibers (67 ± 27 nm) was prepared for the enhanced specific surface area; where polyvinylidene fluoride (PVDF) backbones and the grafted quaternary ammonium moieties (QA; PVDF-g-QA membranes) provided both hydrophobicity and anion-exchange ability (electrostatic interaction). High affinity towards the perfluorooctanoic acid (PFOA)/perfluorooctanesulfonic acid (PFOS) molecules (denoted as PFOX collectively) was observed, and >95% PFOX was removed from synthetic groundwater with a flux of 32.3 Lm(−2)h(−1) at ΔP(o) = 313 Pa. With a higher octanol/water partitioning coefficient (Log K(ow) = 6.3) and close dispersion interaction parameter to the membrane backbones (16.6% difference in δ(d)), the effective PFOS removal remained under alkaline and high conductivity conditions due to the intensive hydrophobic interaction compared to that of PFOA. Long-term studies exhibited >90% PFOX removal in an 8 h test with a capacity of 258 L/m(2). Under mild regeneration conditions, PFOA and PFOS were concentrated by 35-fold and 39-fold, respectively. Overall, the gravity-driven electrospun PVDF-g-QA membranes, with adsorptive effectiveness and ease of regeneration, showed great potential in PFAS remediation.

Selective separation of small molecules by membranes is inhibited by the performance gap between nanofiltration and ultrafiltration membranes. In this work, a membrane that can efficiently remove small molecules (> 300 Da) was created by incorporating graphene oxide quantum dots (GQDs) into a cellulose membrane using an ionic liquid (1-ethyl-3-methylimidazolium acetate). Incorporation of GQD into cellulose membranes using an ionic liquid brings several advantages over traditional mixed matrix membranes: 1) GQDs are abundant in peripheral hydroxyl and carboxyl groups, thus GQDs have strong binding with cellulose through hydrogen bonding and forms a stable composite membrane. 2) Negative surface charge of GQDs helps prevent aggregation. 3) The size (5 nm) of GQD is smaller than most nanoparticles used in membranes, allowing for interesting pore forming properties. GQD-cellulose membranes were prepared by non-solvent induced phase separation in water. It was determined that about 45% of GQDs are incorporated from solution to membrane. GQDs were determined to be located on the membrane surface, giving the membrane negative surface charge and improved hydrophilicity. GQDs showed no leaching after convective flow through the membrane. Impact of GQD on membrane permeability and rejection was studied through convective flow experiments, and through longer term permeability studies.

Oil industries generate large amounts of produced water containing organic contaminants, such as naphthenic acids (NA) and very high concentrations of inorganic salts. Recovery of potable water from produced water can be highly energy intensive is some cases due to its high salt concentration, and safe discharge is more suitable. Here, we explored catalytic properties of iron oxide (FexOy nanoparticles) functionalized membranes in oxidizing NA from water containing high concentrations of total dissolved solids (TDS) using persulfate as an oxidizing agent. Catalytic decomposition of persulfate by FexOy functionalized membranes followed pseudo-first order kinetics with an apparent activation energy of 18 Kcal/mol. FexOy functionalized membranes were capable of lowering the NA concentrations to less than discharge limits of 10 ppm at 40 °C. Oxidation state of iron during reaction was quantified. Membrane performance was investigated for extended period of time. A coupled process of advanced oxidation catalyzed by membrane and nanofiltration was also evaluated. Commercially available nanofiltration membranes were found capable of retaining NA from water containing high concentrations of dissolved salts. Commercial NF membranes, Dow NF270 (Dow), and NF8 (Nanostone) had NA rejection of 79% and 82%, respectively. Retentate for the nanofiltration was further treated with advanced oxidation catalyzed by FexOy functionalized membrane for removal of NA.

Functionalized PVDF membrane platforms were developed for environmentally benign in-situ nanostructured Fe/Pd synthesis and remediation of chlorinated organic compounds. To prevent leaching and aggregation, nanoparticle catalysts were integrated into membrane domains functionalized with poly (acrylic acid). Nanoparticles of 16–19 nm were observed inside the membrane pores by using focused ion beam (FIB). This technique prevents mechanical deformation of the membrane, compared to the normal SEM preparation methods, thus providing a clean, smooth surface for nanoparticles characterization. This allowed quantification of nanoparticle properties (size and distribution) versus depth underneath the membrane surface (0–20 µm). The results showed that nanoparticles were uniformly sized and evenly distributed inside the membrane pores. However, the size of nanoparticles inside the membrane pores was 13.9% smaller than those nanoparticles located on the membrane surface. Investigating nanoparticles inside membrane pores increases the accuracy of kinetic analysis and modeling aspects. Furthermore, the Fe/Pd immobilized membranes showed excellent performance in the degradation of chlorinated organics: Over 96% degradation of 3,3′,4,4′,5-pentachlorobiphenyl (PCB 126) was achieved in less than 15 s residence time in convective flow mode. The regeneration and reuse of this catalytic membrane system were also studied. Particles were examined in XRD upon formation, after deliberate oxidation, and after regeneration. The regenerated sample showed the same crystalline pattern as the original sample. Repeated degradation experiments demonstrated successful PCB 126 dechlorination with nanoparticles regenerated for four cycles with only a small loss in reactivity. It demonstrated that Fe/Pd immobilized membranes have the potential for large-scale remediation applications.

Graphene oxide (GO) membrane has been synthesized on commercial polysulfone ultrafiltration membranes (Pore size: 17 nm) using the drop casting method followed by baking at 90 °C for 24 h. Baking resulted in the reduction of GO and removal of bulk water intercalated in the GO sheets. Deposited GO film showed high stability under shear stress variation. This work shows that water adsorption on the GO membrane determines its permeation performance. Despite the higher viscosity of isopropyl alcohol (IPA), its permeability was 7 times higher than water through the baked (“dry”) GO membranes, which were never contacted with water. However, IPA permeability of GO membranes dropped to 44% (of deionized water) when contacted with water (“hydrated” or “wet” GO membranes). Extensive size exclusion (rejection) studies with various dye and dendrimer molecules showed pore size reduced from 3.3 nm in the “dry” state to 1.3 nm in the “wet” state of GO membranes. FT-IR characterization of GO membrane suggested adsorption of water on the nanochannels of the active layer. Also, significant decay in flux was observed for water (82% of its initial flux) as compared to IPA (38% of its initial flux) for initially dry GO membranes.

An important strategy in the construction of biomimetic membranes and devices is to use natural proteins as the functional components for incorporation in a polymeric or nanocomposite matrix. Toward this goal, an important step is to immobilize proteins with high efficiency and precision without disrupting the protein function. Here, we developed a dual-functional tag containing histidine and the non-natural amino acid azidohomoalanine (AHA). AHA is metabolically incorporated into the protein, taking advantage of the Met-tRNA and Met-tRNA synthetase. Histidine in the tag can facilitate metal-affinity purification, whereas AHA can react with an alkyne-functionalized probe or surface via well-established click chemistry. We tested the performance of the tag using two model proteins, green fluorescence protein and an enzyme pyrophosphatase. We found that the addition of the tag and the incorporation of AHA did not significantly impair the properties of these proteins, and the histidine–AHA tag can facilitate protein purification, immobilization, and labeling.

New and advanced opportunities are arising for the synthesis and functionalization of membranes with selective separation, reactivity, and stimuli-responsive behavior. One such advancement is the integration of bio-based channels in membrane technologies. By a layer-by-layer (LbL) assembly of polyelectrolytes, outer membrane protein F trimers (OmpF) or “porins” from Escherichia coli with central pores ∼2 nm in diameter at their opening and ∼0.7 × 1.1 nm at their constricted region are immobilized within the pores of poly(vinylidene fluoride) microfiltration membranes, in contrast to traditional ruptured lipid bilayer or vesicle processes. These OmpF-membranes demonstrate selective rejection of non-charged organics over ionic solutes, allowing the passage of up to 2 times more salts than traditional nanofiltration membranes starting with rejections of 84% for 0.4 to 1.0 kDa organics. The presence of charged groups in OmpF-membranes also leads to pH-dependent salt rejection through Donnan exclusion. These OmpF-membranes also show exceptional durability and stability, delivering consistent and constant permeability and recovery for over 160 h of operation. Characterization of the solutions containing OmpF and the membranes was conducted during each stage of the process, including detection by fluorescence labelling (FITC), zeta potential, pH responsiveness, flux changes, and rejection of organic–inorganic solutions.

The potential for using hydroxyl radical (OH(•)) reactions catalyzed by iron oxide nanoparticles (NPs) to remediate toxic organic compounds was investigated. Iron oxide NPs were synthesized by controlled oxidation of iron NPs prior to their use for contaminant oxidation (by H(2)O(2) addition) at near-neutral pH values. Cross-linked polyacrylic acid (PAA) functionalized polyvinylidene fluoride (PVDF) microfiltration membranes were prepared by in situ polymerization of acrylic acid inside the membrane pores. Iron and iron oxide NPs (80–100 nm) were directly synthesized in the polymer matrix of PAA/PVDF membranes, which prevented the agglomeration of particles and controlled the particle size. The conversion of iron to iron oxide in aqueous solution with air oxidation was studied based on X-ray diffraction, Mössbauer spectroscopy and BET surface area test methods. Trichloroethylene (TCE) was selected as the model contaminant because of its environmental importance. Degradations of TCE and H(2)O(2) by NP surface generated OH(•) were investigated. Depending on the ratio of iron and H(2)O(2), TCE conversions as high as 100 % (with about 91 % dechlorination) were obtained. TCE dechlorination was also achieved in real groundwater samples with the reactive membranes.

Cellulose-based membrane materials allow for separations in both aqueous solutions and organic solvents. The addition of nanocomposites into cellulose structure is facilitated through steric interaction and strong hydrogen bonding with the hydroxy groups present within cellulose. An ionic liquid, 1-ethyl-3-methylimidazolium acetate, was used as a solvent for microcrystalline cellulose to incorporate graphene oxide quantum dots into cellulose membranes. In this work, other composite materials such as, iron oxide nanoparticles, polyacrylic acid, and lignin sulfonate have all been uniformly incorporated into cellulose membranes utilizing ionic liquid cosolvents. Integration of iron into cellulose membranes resulted in high selectivity (&gt, 99%) of neutral red and methylene blue model dyes separation over salts with a high permeability of 17 LMH/bar. With non-aqueous (alcohol) solvent, iron&ndash, cellulose composite membranes become less selective and more permeable, suggesting the interaction of iron ions cellulose OH groups plays a major role in pore structure. Polyacrylic acid was integrated into cellulose membranes to add pH responsive behavior and capacity for metal ion capture. Calcium capture of 55 mg Ca2+/g membrane was observed for PAA-cellulose membranes. Lignin sulfonate was also incorporated into cellulose membranes to add strong negative charge and a steric barrier to enhance antifouling behavior. Lignin sulfonate was also functionalized on the commercial DOW NF270 nanofiltration membranes via esterification of hydroxy groups with carboxyl group present on the membrane surface. Antifouling behavior was observed for both lignin-cellulose composite and commercial membranes functionalized with lignin. Up to 90% recovery of water flux after repeated cycles of fouling was observed for both types of lignin functionalized membranes while flux recovery of up to 60% was observed for unmodified membranes.

This work deals with the creation of bimetallic thin films on porous polymer membrane surfaces. Metal–polymer composite membranes have been produced through magnetron sputtering. Commercially available membranes with both micrometer and nanometer scale pores were used as supports for deposition. Continuous alloy films of ∼110 nm thickness were deposited to produce the top layer of the composite structure. These films were dealloyed with sulfuric acid creating a nanoporous film structure with a ligament size of 7.7 ± 2.5 nm. The resulting composite membranes were permeable to water at all stages of production, and an polysulfone ultrafiltration membrane with 90 nm of nanoporous Fe/Pd on top showed a flux of 183 L/m2/h (LMH)/bar. The films were evaluated for dechlorination of toxic polychlorinated biphenyls from water. At a loading of 6.6 mg/L Pd attached to 13.2 cm2 support in a 2.5 ppm PCB-1 solution with 1.5 ppm dissolved H2, over 90% of PCB-1 was removed from solution in 30 min, which produced the expec...

This article describes the effects of changing monomer and cross-linker concentrations on the mass gain, water permeability, Pd-Fe nanoparticle (NP) loading, and the rate of degradation of 3,3’,4,4’,5-pentachlorobiphenyl (PCB 126) of pore functionalized polyvinylidene fluoride (PVDF) membranes. In this study, monomer (acrylic acid (AA)) and cross-linker (N, N′- methylene-bis (acrylamide)) concentrations were varied from 10 to 20 wt% of polymer solution and 0.5–2 mol% of monomer concentration, respectively. Results showed that responsive behavior of membrane could be tuned in terms of water permeability over a range of 270–1 L m(−2) h(−1) bar(−1), which is a function of water pH. The NP size on the membrane surface was found in the range of 16–23 nm. With increasing cross-linker density the percentage of smaller NPs (< 10 nm) increases due to smaller mesh size formation during in-situ polymerization of membrane. NP loading was found to vary from 0.21 to 0.94 mg per cm(2) of membrane area depending on the variation of available carboxyl groups in membrane pore domain. The NPs functionalized membranes were then tested for use as a platform for the degradation of PCB 126. The observed batch reaction rate (K(obs)) for PCB 126 degradation for per mg of catalyst loading was found 0.08–0.1 h(−1). Degradation study in convective flow mode shows 98.6% PCB 126 is degraded at a residence time of 46.2 s. The corresponding surface area normalized reaction rate (K(sa)) is found about two times higher than K(sa) of batch degradation; suggesting elimination of the effect of diffusion resistance for degradation of PCB 126 in convective flow mode operation. These Pd-Fe-PAA-PVDF membranes and nanoparticles are characterized by TGA, contact angle measurement, surface zeta potential, XRD, SEM, XPS, FIB, TEM and other techniques reveal the details about the membrane surface, pores and nanoparticles size, shape and size-distribution. Statistical analysis based on experimental results allows us to depict responsive behavior of functionalized membrane. In our best knowledge this paper first time reports detail study on responsive behavior of pore functionalized membrane in terms of permeability, NPs size, metal loading and its effect on PCB 126 degradation in a quantified approach.

The design and understanding of rejection mechanisms for both positively and negatively charged nanofiltration (NF) membranes are needed for the development of highly selective separation of multivalent ions. In this study, positively charged nanofiltration membranes were created via an addition of commercially available polyallylamine hydrochloride (PAH) by conventional interfacial polymerization technique. Demonstration of real increase in surface zeta potential, along with other characterization methods, confirmed the addition of weak basic functional groups from PAH. Both positively and negatively charged NF membranes were tested for evaluating their potential as a technology for the recovery or separation of lanthanide cations (neodymium and lanthanum chloride as model salts) from aqueous sources. Particularly, the NF membranes with added PAH performed high and stable lanthanides retentions, with values around 99.3% in mixtures with high ionic strength (100 mM, equivalent to ~6,000 ppm), 99.3% rejection at 85% water recovery (and high Na(+)/La(3+) selectivity, with 0% Na(+) rejection starting at 65% recovery), and both constant lanthanum rejection and permeate flux at even pH 2.7. Donnan steric pore model with dielectric exclusion elucidated the transport mechanism of lanthanides and sodium, proving the potential of high selective separation at low permeate fluxes using positively charged NF membranes.

Perfluorochemicals (PFCs) are emerging contaminants in various water sources. Responsive polymers provide a new avenue for PFC adsorption/desorption from water. Poly-N-isopropylacrylamide’s (PNIPAm’s) temperature-responsive behavior and hydrophilic/hydrophobic transition is leveraged for reversible adsorption and desorption of PFCs. Adsorption of PFOA (perfluoro-octanoic acid) onto PNIPAm hydrogels yielded Freundlich distribution coefficients (K(d)) of 0.073 L/g at 35 °C (above LCST) and 0.026 L/g at 22°C. Kinetic studies yielded second order rate constants (k(2)) of 0.012 g/mg/h for adsorption and 12.6 g/mg/h for desorption, with initial rates of 28 mg/g/h and 41 mg/g/h, respectively. Interaction parameters of PNIPAm’s functional groups in its different conformational states, as well as the hydrophobic fluorinated carbon tails and hydrophilic head groups of PFOA are used to describe relative adsorption. Polyvinylidene difluoride (PVDF) provides a robust membrane structure for the commercial viability of polymeric adsorbents. Temperature swing adsorption of PFOA using PNIPAm functionalized PVDF membrane pores showed consistent adsorption and desorption capacity over 5 cycles. PFOA desorption percentage of 60% was obtained in pure water at temperatures below PNIPAm’s lower critical solution temperature (LCST) while 13% desorption was obtained at temperatures above the LCST, thus showing the importance of the LCST on desorption performance.

Selective separation of lignin depolymerization products is key to fractionating and isolating high-value aromatic compounds from the depolymerization process. The primary aim of this study was to synthesis graphene oxide (GO) membranes for selective separations of lignin oligomeric units from polar organic solvent-water media. GO membranes were synthesized on a polymeric substrate by a shear assisted casting of aqueous GO dispersion using a wire-wound rod. Deposited GO was then reduced to different extents by controlled thermal incubation, and the impact on membrane performance was investigated. The extent of reduction of GO was established by extensive characterization with FTIR, XPS, Raman Spectroscopy, XRD, and contact angle measurements. Impressive performance with the rejection of over 70% for the model compound trimer BMP (2,6-bis[(2-hydroxy-5-methyl phenyl) methyl]-4-methylphenol) was achieved compared to only 20% rejection for the dimer GGE (guaiacylglycerol-β-guaiacylether) with isopropanol-water (90–10% by volume) as a solvent. This corresponds to an encouraging selective separation with selective permeation of dimer (GGE) 3.5 times higher compared to trimer (BMP). rGO membranes exhibited a stable performance over 84 h of operation at a shear rate of 1.1 Pa in a cross-flow mode of operation. Selective separation of GO can be effectively modulated by controlling the O/C ratio by the extent of reduction of GO; indeed, the retention of trimeric compounds increased with increasing GO reduction. The remarkable performance of GO membranes could enable energy-efficient fractionation of lignin oligomeric compounds from polar organic solvents.

The poly(methacrylic acid) (PMAA) was synthesized in the pores of commercial microfiltration PVDF membranes to allow incorporation of catalytic palladium/iron (Pd/Fe) nanoparticles for groundwater remediation. Particles of 17.1 ± 4.9 nm size were observed throughout the pores of membranes using a focused ion beam. To understand the role of Pd fractions and particle compositions, 2-chlorobiphenyl was used as a model compound in solution phase studies. Results show H(2) production (Fe(0) corrosion in water) is a function of Pd coverage on the Fe. Insufficient H(2) production caused by higher coverage (> 10.4% for 5.5 wt%) hindered dechlorination rate. With 0.5 wt% Pd, palladized-Fe reaction rate (surface area normalized reaction rate, k(sa) = 0.12 L/(m(2)-h) was considerably higher than isolated Pd and Fe particles. For groundwater, in a single pass of Pd/Fe-PMAA-PVDF membranes (0.5 wt% Pd), chlorinated organics, such as trichloroethylene (177 ppb) and carbon tetrachloride (35 ppb), were degraded to 16 and 0.3 ppb, respectively, at 2.2 seconds of residence time. The degradation rate (observed k(sa)) followed the order of carbon tetrachloride > trichloroethylene > tetrachloroethylene > chloroform. A 36 h continuous flow study with organic mixture and the regeneration process show the potential for on-site remediation.

Solvent transport in membranes composed of stacked sheets of graphene oxide (GO) with molecular scale channels and a complex arrangement of hydrophobic and hydrophilic domains is not well understood. Here, we observe that the interlayer space between GO sheets expands in different solvents without disturbing the membrane integrity and is typically larger in aqueous media compared to nonaqueous media. However, the membranes have a tighter molecule sieving feature in aqueous media as demonstrated by lower permeance and higher solute rejection arising from interfacial water layers "sticking" to charged polar groups. As a result of this polar interaction, the permeance of polar solvents in GO membrane scales inversely to the polarity of the solvent, which is contrary to other polymeric and ceramic hydrophilic membranes and also scales inversely to the viscosity of solvents as per continuum expectations. We highlight the extended solvent-handling space of GO membranes, such as in polar protic, polar aprotic, and nonpolar solvents, demonstrating versatility over a commercial nanofiltration membrane, and we predict exciting new applications in advanced separation engineering.

Membranes have been widely used in water remediation (e.g. desalination and heavy metal removal) because of the ability to control membrane pore size and surface charge. The incorporation of nanomaterials into the membranes provides added benefits through increased reactivity with different functionality. In this study, we report the dechlorination of 2-chlorobiphenyl in the aqueous phase by a reactive membrane system. Fe/Pd bimetallic nanoparticles (NPs) were synthesized (in-situ) within polyacrylic acid (PAA) functionalized polyvinylidene fluoride (PVDF) membranes for degradation of polychlorinated biphenyls (PCBs). Biphenyl formed in the reduction was further oxidized into hydroxylated biphenyls and benzoic acid by an iron-catalyzed hydroxyl radical (OH•) reaction. The formation of magnetite on Fe surface was observed. This combined pathway (reductive/oxidative) could reduce the toxicity of PCBs effectively while eliminating the formation of chlorinated degradation byproducts. The successful manufacturing of full-scale functionalized membranes demonstrates the possibility of applying reactive membranes in practical water treatment.

A new class of bimetallic materials based on palladium-decorated iron nanotubes is described that demonstrates high reactivity in dechlorination reactions. This high dechlorination efficiency was attributed to the high surface area to volume ratio of the hollow nanotubes structure. Herein, we evaluated the effect of different conditions, such as the nanotube size, and the palladium loading on the efficiency of the dechlorination of PCB 77, a model coplanar polychlorinated biphenyl (PCB), by the Pd/Fe bimetallic nanotubes system. The efficiency of the dechlorination was lowered by decreasing the tube diameter from 200 to 100 nm. In addition, the interior surface as well as the exterior surface of the as-synthesized Pd/Fe bimetallic nanotubes was found to contribute to the high efficiency of the dechlorination of PCB 77. The dechlorination of PCB 77 by Pd/Fe bimetallic nanotubes demonstrated small activation energy indicating diffusion controlled reaction. The as-prepared Pd/Fe bimetallic nanotubes showed extended lifetime activity when used in multiple dechlorination cycles.

Persistent organic pollutants such as polychlorinated biphenyls (PCBs) are associated with detrimental health outcomes including cardiovascular diseases. Remediation of these compounds is a critical component of environmental policy. Although remediation efforts aim to completely remove toxicants, little is known about the effects of potential remediation byproducts. We previously published that Fe/Pd nanoparticles effectively dechlorinate PCB 77 to biphenyl, thus eliminating PCB-induced endothelial dysfunction using primary vascular endothelial cells. Herein, we analyzed the toxic effects of PCB congener mixtures (representative mixtures of commercial PCBs based on previous dechlorination data) produced at multiple time points during the dechlorination of PCB 77 to biphenyl. Compared with pure PCB 77, exposing endothelial cells to lower chlorinated PCB byproducts led to improved cellular viability, decreased superoxide production, and decreased nuclear factor kappa B activation based on duration of remediation. Presence of the parent compound, PCB 77, led to significant increases in mRNA and protein inflammatory marker expression. These data implicate that PCB dechlorination reduces biological toxicity to vascular endothelial cells.

Covalent bonding of graphene oxide quantum dots (GOQDs) onto amino modified polyvinylidene fluoride (PVDF) membrane has generated a new type of nano-carbon functionalized membrane with significantly enhanced antibacterial and antibiofouling properties. A continuous filtration test using E. coli containing feedwater shows that the relative flux drop over GOQDs modified PVDF is 23%, which is significantly lower than those over pristine PVDF (86%) and GO-sheet modified PVDF (62%) after 10 h of filtration. The presence of GOQD coating layer effectively inactivates E. coli and S. aureus cells and prevents the biofilm formation on the membrane surface, producing excellent antimicrobial activity and potentially antibiofouling capability, more superior than those of previously reported two-dimensional GO sheets and one-dimensional CNTs modified membranes. The distinctive antimicrobial and antibiofouling performances could be attributed to the unique structure and uniform dispersion of GOQDs, enabling the exposure of a larger fraction of active edges and facilitating the formation of oxidation stress. Furthermore, GOQDs modified membrane possesses satisfying long-term stability and durability due to the strong covalent interaction between PVDF and GOQDs. This study opens up a new synthetic avenue in the fabrication of efficient surface-functionalized polymer membranes for potential waste water treatment and biomolecules separation.