Production of Stable Electrically Conductive PVDF Membranes Based on Polydopamine-Polyethyleneimine-Assisted Deposition of Carbon Nanotubes.

Electrically conductive membranes (ECMs) have emerged as a multifunctional separation technology that integrates membrane filtration with electrochemical reactions. Physical stability remains a critical challenge for ECMs synthesized by coating polymer membranes with conductive materials. In this article, polydopamine (PDA) and polyethyleneimine (PEI) were used to facilitate the synthesis of significantly more stable ECMs using poly(vinylidene fluoride) (PVDF) ultrafiltration membranes and carbon nanotubes (CNTs). Four different synthesis methods were compared in terms of the final surface stability and separation properties: (1) CNTs deposited on PEI-crosslinked PDA-coated PVDF membranes, (2) PEI-crosslinked CNTs deposited on PDA-coated PVDF, (3) PDA, PEI and CNTs sequentially deposited layer-by-layer on PVDF, and (4) PEI-crosslinked PDA deposited on CNT-coated PVDF. The results revealed that method 1 generated ECMs with the greatest physical stability, highest electrical conductivity (18,518 S/m), and sufficient permeability (395.2 L/(m2·h·bar). In comparison, method 2 resulted in membranes with the highest permeability (2128.5 L/(m2·h·bar), but with low surface conductivity (502 S/m) and poor physical stability (i.e., 53-75% lower peel-off forces compared to other methods). Overall, methods 1, 3, and 4 can be used to make highly conductive membranes with a 97-99% removal of methyl orange by electrochemical degradation at -3 V.

Wettability Alteration of a Thiolene-Based Polymer (NOA81): Surface Characterization and Fabrication Techniques.

Wettability plays a significant role in controlling multiphase flow in porous media for many industrial applications, including geologic carbon dioxide sequestration, enhanced oil recovery, and fuel cells. Microfluidics is a powerful tool to study the complexities of interfacial phenomena involved in multiphase flow in well-controlled geometries. Recently, the thiolene-based polymer called NOA81 emerged as an ideal material in the fabrication of microfluidic devices, since it combines the versatility of conventional soft photolithography with a wide range of achievable wettability conditions. Specifically, the wettability of NOA81 can be continuously tuned through exposure to UV-ozone. Despite its growing popularity, the exact physical and chemical mechanisms behind the wettability alteration have not been fully characterized. Here, we apply different characterization techniques, including contact angle measurements, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM) to investigate the impact of UV-ozone on the chemical and physical properties of NOA81 surfaces. We find that UV-ozone exposure increases the oxygen-containing polar functional groups, which enhances the surface energy and hydrophilicity of NOA81. Additionally, our AFM measurements show that spin-coated NOA81 surfaces have a roughness less than a nanometer, which is further reduced after UV-ozone exposure. Lastly, we extend NOA81 use cases by creating (i) 2D surface with controlled wettability gradient and (ii) a 3D column packed with monodisperse NOA81 beads of controlled size and wettability.

Nanocomposite Polymeric Membranes for Organic Micropollutant Removal: A Critical Review.

The prevalence of organic micropollutants (OMPs) and their persistence in water supplies have raised serious concerns for drinking water safety and public health. Conventional water treatment technologies, including adsorption and biological treatment, are known to be insufficient in treating OMPs and have demonstrated poor selectivity toward a wide range of OMPs. Pressure-driven membrane filtration has the potential to remove many OMPs detected in water with high selectivity as a membrane's molecular weight cutoff (MWCO), surface charge, and hydrophilicity can be easily tailored to a targeted OMP's size, charge and octanol-water partition coefficient (Kow). Over the past 10 years, polymeric (nano)composite microfiltration (MF), ultrafiltration (UF), and nanofiltration (NF) membranes have been extensively synthesized and studied for their ability to remove OMPs. This review discusses the fate and transport of emerging OMPs in water, an assessment of conventional membrane-based technologies (NF, reverse osmosis (RO), forward osmosis (FO), membrane distillation (MD) and UF membrane-based hybrid processes) for their removal, and a comparison to the state-of-the-art nanoenabled membranes with enhanced selectivity toward specific OMPs in water. Nanoenabled membranes for OMP treatment are further discussed with respect to their permeabilities, enhanced properties, limitations, and future improvements.

Assessing leached TOC, nutrients and phenols from peatland soils after lab-simulated wildfires: Implications to source water protection.

Pollutant leaching from wildfire-impacted peatland soils (peat) is well-known, but often underestimated when considering boreal ecosystem source water protection and when treating source waters to provide clean drinking water. Burning peat impacts its physical properties and chemical composition, yet the consequences of these transformations to source water quality through pollutant leaching has not been studied in detail. We combusted near-surface boreal peat under simulated peat smoldering conditions at two temperatures (250 °C and 300 °C) and quantified the concentrations of the leached carbon, nutrients and phenols from 5 g peat L-1 reverse osmosis (RO) water suspensions over a 2-day leaching period. For the conditions studied, measured water quality parameters exceeded US surface water guidelines and even exceeded EU and Canadian wastewater/sewer discharge limits including chemical oxygen demand (COD) (125 mg/L), total nitrogen (TN) (15 mg/L), and total phosphorus (TP) (2 mg/L). Phenols were close to or higher than the suggested water supply standard established by US EPA (1 mg/L). Leached carbon, nitrogen and phosphorus mainly came from the organic fraction of peats. Heating peats to 250 °C promoted the leaching of carbon-related pollutants, whereas heating to 300 °C enhanced the leaching of nutrients. Post-heated peats leached higher loads of pollutants in water than pre-heated peats, suggesting that fire-damaged boreal peats may be a critical but underappreciated source of water pollution. A simplified Partial Least Squares (PLS) model based on other easily measured parameters provided a simple method for determining the extent of COD and phenolic pollution in bulk water, relevant for water and wastewater treatment plants. Conclusions from this lab study indicate the need for field measurements of aquatic pollutants downstream of peatland watersheds post-fire as well as increased monitoring and treatment of potable water sources for leachable micropollutants in fire-dominated forested peatlands.

Mixed metal oxide anodes used for the electrochemical degradation of a real mixed industrial wastewater.

Mixed industrial wastewaters are often highly contaminated with heavy metals and organic pollutants. Treating these mixed wastewaters requires many stagewise unit operations. Our work investigates using an electrochemical oxidation-in-situ coagulation (ECO-IC) process as a pre-treatment step toward the efficient treatment of real mixed industrial wastewater rich with heavy metals and organic contaminants. The process degraded organic contaminants in the wastewater via anodic electrochemical oxidation. Simultaneously, heavy metals were precipitated in the solution by coagulants (iron hydroxides) formed in-situ by cathode-generated hydroxyl ions reacting with the significant amounts of dissolved iron in the wastewater. IrO2-RuO2 mixed metal oxide anodes were identified as the best electrodes for organic compound degradation demonstrating 97% degradation of methyl orange (MO) as a model compound within 15 min. These anodes were used to treat real industrial wastewater produced from the industrial cleaning of train tanker cars transporting industrial solvents. The electrochemical treatment experiments resulted in a treated solution with a lower heavy metal content, achieving 96% reduction in Fe and 30% reduction in As content. Only moderate decreases in organic content were observed up to a maximum of 13% reduction in total organic carbon after 1 h of treatment. Electrochemical treatment of the mixed industrial wastewater produced greater effective diameter of the suspended particles and distinct sediment, liquid, and suspended foam phases that could be easily separated for further treatment. ECO-IC shows promise as an efficient and chemical-free method to coagulate heavy metals in real industrial wastewaters and could be an effective pre-treatment in their separation.

Navigating Performance Standards for Face Mask Materials: A Custom-Built Apparatus for Measuring Particle Filtration Efficiency.

Public health agencies have recommended the community use of face masks to reduce the transmission of airborne diseases like COVID-19. Virus transmission is reduced when masks act as efficient filters, thus evaluating mask particle filtration efficiency (PFE) is essential. However, the high cost and long lead times associated with purchasing turn-key PFE systems or hiring certified laboratories hampers the testing of filter materials. There is a clear need for "custom" PFE test systems; however, the variety of standards that prescribe (medical) face mask PFE testing (e.g., ASTM International, NIOSH) vary widely in their protocols and clarity of guidelines. Herein, the development is described of an "in-house" PFE system and method for testing face masks in the context of current standards for medical masks. Pursuant to the ASTM International standards, the system uses an aerosol of latex spheres (0.1 µm nominal size) with particle concentrations upstream and downstream of the mask material measured using a laser particle analyzer. PFE measurements are obtained for a variety of common fabrics and medical masks. The approach described in this work conforms to the current standards for PFE testing while providing the flexibility to adapt to changing needs and filtration conditions.

Fast synthesis of high surface area bio-based porous carbons for organic pollutant removal.

A fast, facile and one-pot chemical activation method was used to develop porous carbons with high surface area and excellent phenolic micropollutant adsorption performance from renewable precursors. This method was applied to three precursors: naturally abundant, but often underestimated wildfire-damaged boreal peats, corn starch, and cellulose. Porous carbon formation was accomplished through precursor impregnation with ZnCl2 powder and their simultaneous pyrolysis under inert N2 flow at 400 or 600 °C for 1 h. The maximum adsorption capacities of these bio-sorbents towards a model contaminant, p-nitrophenol, in simulated wastewater were equal to or superior than using a commercial activated carbon (CAC), Norit GSX (> 530 mg/g) over wide initial concentration ranges (20-2000 mg/L). p-nitrophenol adsorption best fitted Freundlich and Redlich-Peterson isotherms, suggesting multilayer chemisorption. Low concentration p-nitrophenol (20 mg/L) adsorption into the bio-sorbents was rapid in the first 4 h, and could reach high removals (> 98%). The method presented here yielded bio-sorbents with similarly high adsorption performance regardless of the precursor type, while avoiding energy-intensive processing steps during sorbent production. This study gives a useful alternative for manufacturing new sorbents from other upcycled carbonaceous and/or bio-based materials to remove micropollutants and heavy metals.•Fast, single-step chemical activation for manufacturing bio-based porous carbons.•Efficient adsorption towards aqueous phenolic micropollutant from batch studies.•A competitive substitute of charcoal activated carbons for water purification.

Simultaneous Dechlorination and Advanced Oxidation Using Electrically Conductive Carbon Nanotube Membranes.

Electrically conductive membranes have shown significant promise in combining conventional separations with in situ contaminant oxidation, but little has been done to consider chlorine removal. This study demonstrates the simultaneous chlorine removal and oxidation of organic compounds during filtration using an electrochemically assisted electrically conductive carbon nanotube (CNT) membrane. As much as 80% of chlorine was removed in the feed by CNT membranes at the initial phase of continuous filtration. The efficacy of these CNT membranes toward chlorine removal was dependent on the mass of CNTs within the membranes and the applied pressure to the membranes, indicating the central role of available CNT active sites and sufficient reaction time. Furthermore, the removal mechanism of chlorine by CNTs was revealed by studying the degradation of benzoic acid and cyclic voltammetry on the membrane surface. Reactive oxidants were generated by the reductive decomposition of chlorine through the catalytic interaction with CNTs. Subsequently, electrical potentials were applied to the CNT membrane surfaces during the filtration of chlorinated feed waters. The simultaneous decomposition of chlorine and oxidation of benzoic acid were significantly enhanced by applying a cathodic current to CNT membranes enabling continuous dechlorination. The cathodic current applied to CNT membranes is believed to regenerate CNT membranes by providing electrons for the reductive decomposition of chlorine. In situ chemical-free dechlorination coupled with membrane filtration offers great opportunity to reducing the environmental impact of desalination, while maximizing the lifetime of reverse osmosis membranes and demonstrating greener approaches available to industrial water treatment.

CNT-sorbents for heavy metals: Electrochemical regeneration and closed-loop recycling.

Heavy metal contamination of aquatic environments is a major concern. Carbon nanotubes (CNTs) are among the most effective adsorbents for heavy metal removal due. However, their high cost and their uncertain environmental impact necessitates a closed-loop process through sorbent regeneration and recycling for practical application. Our work demonstrates heavy metal adsorption by carboxylic acid-functionalized single-walled/double-walled carbon nanotubes (f-SW/DWCNTs) and their regeneration using electric fields. We follow a multi-step process: 1) copper in an aqueous solution is adsorbed onto the surface of f-SW/DWCNTs, 2) the copper-saturated f-SW/DWCNTs are filtered onto a microfiltration (MF) membrane, 3) the f-SW/DWCNT coated membrane is used as an anode in an electrochemical cell, 4) an applied electric field desorbs the metals from the CNTs into a concentrated waste, and 5) the CNTs are separated from the membrane, re-dispersed and reused in copper-contaminated water for successive adsorption. With an applied positive electric potential, we achieved ∼90 % desorption of Cu from f-SW/DWCNTs. We hypothesize that the electric field generated at the anode causes electrostatic repulsion between the anode and the electrostatically adsorbed heavy metal ions. The effect of applied voltages, electrode spacing and electrolyte conductivity on the desorption of Cu from CNTs was also investigated.

Hydrophobicity of peat soils: Characterization of organic compound changes associated with heat-induced water repellency.

Boreal peatlands provide critical global and regional ecosystem functions including climate regulation and nutrient and water retention. Wildfire represents the largest disturbance to these ecosystems. Peatland resilience depends greatly on the extent of post-fire peat soil hydrophobicity. Climate change is altering wildfire intensity and severity and consequently impacting post-fire peat soil chemistry and structure. However, research on fire-impacted peatlands has rarely considered the influence of peat soil chemistry and structure on peatland resilience. Here we characterized the geochemical and physical properties of natural peat soils under laboratory heating conditions. The general trend observed is that hydrophilic peat soils become hydrophobic under moderate heating and then become hydrophilic again after heating for longer, or at higher, temperatures. The loss of peat soil hydrophilicity initially occurs due to evaporative water loss (250 °C and 300 °C for <5 min). Gently but thoroughly dried peat soils (105 °C for 24 h) also show mass losses after heating, indicating the loss of organic compounds through thermal degradation. Gas chromatography-mass spectrometry (GC-MS) and Fourier transform infrared (FTIR) spectroscopy were used to characterize the chemistry of unburned and 300 °C burned peat soils, and various fatty acids, polycyclic compounds, saccharides, aromatic acids, short-chain molecules, lignin and carbohydrates were identified. We determined that the heat-induced degradation of polycyclic compounds and aliphatic hydrocarbons, especially fatty acids, caused dried, hydrophobic peat soils to become hydrophilic after only 20 min of heating at 300 °C. Furthermore, peat soils became hydrophilic more quickly (20 min vs 6 h) with an increase in heat from 250 °C to 300 °C. Minimal structural changes occurred, as characterized by BET and SEM analyses, confirming that surface chemistry, in particular fatty acid content, rather than structure govern changes in peat soil hydrophobicity.

Cellulose nanocrystal zero-valent iron nanocomposites for groundwater remediation.

Zero-valent iron nanoparticles (nano-ZVIs) have been widely studied for in situ remediation of groundwater and other environmental matrices. Nano-ZVI particle mobility and reactivity are still the main impediments in achieving efficient in situ groundwater remediation. Compared to the nano-ZVI "coating" strategy, nano-ZVI stabilization on supporting material allows direct contact with the contaminant, reduces the electron path from the nano-ZVI to the target contaminant and increases nano-ZVI reactivity. Herein, we report the synthesis of nano-ZVI stabilized by cellulose nanocrystal (CNC) rigid nanomaterials (CNC-nano-ZVI; Fe/CNC = 1 w/w) with two different CNC functional surfaces (-OH and -COOH) using a classic sodium borohydride synthesis pathway. The final nanocomposites were thoroughly characterized and the reactivity of CNC-nano-ZVIs was assessed by their methyl orange (MO) dye degradation potential. The mobility of nanocomposites was determined in (sand/glass bead) porous media by utilizing a series of flowthrough transport column experiments. The synthesized CNC-nano-ZVI provided a stable colloidal suspension and demonstrated high mobility in porous media with an attachment efficiency (α) value of less than 0.23. In addition, reactivity toward MO increased up to 25% compared to bare ZVI. The use of CNC as a delivery vehicle shows promising potential to further improve the capability and applicability of nano-ZVI for in situ groundwater remediation and can spur advancements in CNC-based nanocomposites for their application in environmental remediation.

Thermochemical Analysis of Molybdenum Thin Films on Porous Alumina.

Molybdenum (Mo) thin films (thickness <100 nm) were physically deposited by e-beam evaporation on a porous alumina substrate and were analyzed for their stability and reactivity under various thermal and gas conditions. The Mo thin-film composites were stable below 300 °C but had no reactivity toward gases. Mo thin films showed nitrogen incorporation on the surface as well as in the subsurface at 450 °C, as confirmed by X-ray photoelectron spectroscopy. The reactivity toward nitrogen was diminished in the presence of CO2, although no carbon species were detected either on the surface or in the subsurface. The Mo thin films have a very stable native oxide layer, which may further oxidize to higher oxidation states above 500 °C due to the reaction with the porous anodized alumina substrate. The oxidation of Mo thin films was accelerated in the presence of oxidizing gases. At 600 °C in N2, the Mo thin film on anodized alumina was completely oxidized and may also have been volatilized. The results imply that choosing thermally stable and inactive porous supports and operating in nonoxidizing conditions below 500 °C will likely maintain the stability of the Mo composite. This study provides key information about the chemical and structural stability of a Mo thin film on a porous substrate for future membrane applications and offers further insights into the integrity of thin-film composites when exposed to harsh conditions.

Improved chlorine tolerance of a polyvinyl pyrrolidone-polysulfone membrane enabled by carboxylated carbon nanotubes.

Chemical cleaning of membranes may be limited by the tolerance of some polymeric membranes to chlorine. In this work we show that modification of a polyvinyl pyrrolidone-polysulfone (PVP-PSF) membrane with carboxylated carbon nanotubes (CNTs) leads to greater chlorine tolerance of the membrane along with smoothing the surface roughness and improving some membrane properties including permeability, hydrophilicity and antifouling ability. In comparison with PVP-PSF membrane, incorporating carboxylated CNTs reduced the release of organic matter from the membrane and caused less decrease in hydrophilicity, permeability and BSA rejection. After chlorine treatment of a conventional PVP-PSF membrane, an infrared absorbance peak around 1670 cm-1, representing the vibration of the amide bond in the PVP, decreased significantly and two smaller peaks at around 1725 and 1775 cm-1 were observed. The percentage of C-Cl (2p) in the PVP-PSF membrane was about 2.8 times greater than that of the carboxylated CNT-composite PVP-PSF (CNT-PVP-PSF) membrane after chlorine exposure, suggesting greater chlorine tolerance of CNT-PVP-PSF membrane. In comparison with PVP-PSF membrane, the formation of toxic chlorinated byproducts during chlorination of organic matter released from CNT-PVP-PSF membrane was much lower. The improvement of tolerance to chlorine is attributed to stabilization of the polymer through hydrogen bonding between polymer and carboxylated CNTs.

Cellulose nanomaterials in water treatment technologies.

Cellulose nanomaterials are naturally occurring with unique structural, mechanical and optical properties. While the paper and packaging, automotive, personal care, construction, and textiles industries have recognized cellulose nanomaterials' potential, we suggest cellulose nanomaterials have great untapped potential in water treatment technologies. In this review, we gather evidence of cellulose nanomaterials' beneficial role in environmental remediation and membranes for water filtration, including their high surface area-to-volume ratio, low environmental impact, high strength, functionalizability, and sustainability. We make direct comparison between cellulose nanomaterials and carbon nanotubes (CNTs) in terms of physical and chemical properties, production costs, use and disposal in order to show the potential of cellulose nanomaterials as a sustainable replacement for CNTs in water treatment technologies. Finally, we comment on the need for improved communication and collaboration across the myriad industries invested in cellulose nanomaterials production and development to achieve an efficient means to commercialization.

Aquatic biofouling prevention by electrically charged nanocomposite polymer thin film membranes.

Electrically conductive polymer-nanocomposite (ECPNC) tight nanofiltration (NF) thin film membranes were demonstrated to have biofilm-preventing capabilities under extreme bacteria and organic material loadings. A simple route to the creation and application of these polyamide-carbon nanotube thin films is also reported. These thin films were characterized with SEM and TEM as well as FTIR to demonstrate that the carbon nanotubes are embedded within the polyamide and form ester bonds with trimesoyl chloride, one of the monomers of polyamide. These polymer nanocomposite thin film materials boast high electrical conductivity (∼400 S/m), good NaCl rejection (>95%), and high water permeability. To demonstrate these membranes' biofouling capabilities, we designed a cross-flow water filtration vessel with insulated electrical leads connecting the ECPNC membranes to an arbitrary waveform generator. In all experiments, conducted in highly bacterially contaminated LB media, flux tests were run until fluxes decreased by 45 ± 3% over initial flux. Biofilm-induced, nonreversible flux decline was observed in all control experiments and a cross-flow rinse with the feed solution failed to induce flux recovery. In contrast, flux decrease for the ECPNC membranes with an electric potential applied to their surface was only caused by deposition of bacteria rather than bacterial attachment, and flux was fully recoverable following a short rinse with the feed solution and no added cleaning agents. The prevention of biofilm formation on the ECPNC membranes was a long-term effect, did not decrease with use, and was highly reproducible.

Comprehensive examination of mesophases formed by DMPC and DHPC mixtures.

Mixtures of long- and short-chain phospholipids, specifically 14:0 and 6:0 phosphatidylcholines (DMPC and DHPC), have been used successfully in NMR studies as magnetically alignable substrates for membrane-associated proteins. However, recent publications have shown that the phase behavior of these mixtures is much more complex than originally thought. Using polarized light microscopy and small-angle neutron scattering, phase diagrams of DMPC/DHPC mixtures at molar ratios of 2, 3.2, and 5 have been determined. Generally, at temperatures below the main-chain melting transition of DMPC (T(M) = 23 degrees C), an isotropic phase of disk-like micelles is found. At high temperatures (T > 50 degrees C), a lamellar phase consisting of either multilamellar vesicles (MLV) or extended lamellae is formed, which at low lipid concentrations (e.g., MLV) coexists with an excess of water. At intermediate temperatures and lipid concentrations, a chiral nematic phase made up of worm-like micelles was observed.