Surface modification of membranes is an effective approach for imparting unique characteristics and additional functionalities to the membranes. Chemical grafting is a commonly used membrane modification technique due to its versatility in tailoring and optimizing the membrane surface with desired functionalities. Various types of polymers can be precisely grafted onto the membrane surface and the operating conditions of grafting can be tailored to further fine-tune the membrane surface properties. This review focuses on the recent strategies in improving the surface design of liquid separation membranes through grafting-from technique, also known as graft polymerization, to improve membrane performance in wastewater treatment and desalination applications. An overview on membrane technology processes such as pressure-driven and osmotically driven membrane processes are first briefly presented. Grafting-from surface chemical modification approaches including chemical initiated, plasma initiated and UV initiated approaches are discussed in terms of their features, advantages and limitations. The innovations in membrane surface modification techniques based on grafting-from techniques are comprehensively reviewed followed by some highlights on the current challenges in this field. It is concluded that grafting-from is a versatile and effective technique to introduce various functional groups to enhance the surface properties and separation performances of liquid separation membranes.
In this study, biopolymer composite electrolytes based on chitosan:ammonium iodide:Zn(II)-complex plasticized with glycerol were successfully prepared using the solution casting technique. Various electrical and electrochemical parameters of the biopolymer composite electrolytes' films were evaluated prior to device application. The highest conducting plasticized membrane was found to have a conductivity of 1.17 × 10-4 S/cm. It is shown that the number density, mobility, and diffusion coefficient of cations and anions fractions are increased with the glycerol amount. Field emission scanning electron microscope and Fourier transform infrared spectroscopy techniques are used to study the morphology and structure of the films. The non-Debye type of relaxation process was confirmed from the peak appearance of the dielectric relaxation study. The obtained transference number of ions (cations and anions) and electrons for the highest conducting sample were identified to be 0.98 and 0.02, respectively. Linear sweep voltammetry shows that the electrochemical stability of the highest conducting plasticized system is 1.37 V. The cyclic voltammetry response displayed no redox reaction peaks over its entire potential range. It was discovered that the addition of Zn(II)-complex and glycerol plasticizer improved the electric double-layer capacitor device performances. Numerous crucial parameters of the electric double-layer capacitor device were obtained from the charge-discharge profile. The prepared electric double-layer capacitor device showed that the initial values of specific capacitance, equivalence series resistance, energy density, and power density are 36 F/g, 177 Ω, 4.1 Wh/kg, and 480 W/kg, respectively.
In the present work, a highly efficient mixed matrix membrane (MMM) for humic acid (HA) removal was developed. Multiwalled carbon nanotubes (MWCNTs) were functionalized in the presence of 3-methacryloxypropyl trimethoxysilane using the co-condensation method and were subsequently loaded with TiO2 (prepared via the sol-gel route). The as-prepared material was then incorporated into a PES polymer solution to prepare a fMWCNT-TiO2/PES hybrid membrane via non-solvent induced phase inversion. The microstructure of the membrane was characterized using Fourier transform infrared spectroscopy, atomic force microscopy, scanning electron microscopy, water contact angle, thickness, porosity, and pore size. The fMWCNT-TiO2/PES hybrid membrane was tested for the removal of HA and antifouling performance. The results show that the surface hydrophilicity of the membranes was greatly improved upon the addition of the fMWCNT-TiO2 particles. The results show that 92% of HA was effectively removed after 1 h of filtration. In comparison with pristine membrane, the incorporation of fMWCNT-TiO2 nanoparticles led to enhanced pure water flux (99.05 L/m2 h), permeate flux (62.01 L/m2 h), higher HA rejection (92%), and antifouling improvement (RFR: 37.40%, FRR: 86.02%). Thus, the fMWCNT-TiO2/PES hybrid membrane is considered to be a great potential membrane for the improvement of ultrafiltration membranes.
Vacuum membrane distillation (VMD) has attracted increasing interest for various applications besides seawater desalination. Experimental testing of membrane technologies such as VMD on a pilot or large scale can be laborious and costly. Machine learning techniques can be a valuable tool for predicting membrane performance on such scales. In this work, a novel hybrid model was developed based on incorporating a spotted hyena optimizer (SHO) with support vector machine (SVR) to predict the flux pressure in VMD. The SVR-SHO hybrid model was validated with experimental data and benchmarked against other machine learning tools such as artificial neural networks (ANNs), classical SVR, and multiple linear regression (MLR). The results show that the SVR-SHO predicted flux pressure with high accuracy with a correlation coefficient (R) of 0.94. However, other models showed a lower prediction accuracy than SVR-SHO with R-values ranging from 0.801 to 0.902. Global sensitivity analysis was applied to interpret the obtained result, revealing that feed temperature was the most influential operating parameter on flux, with a relative importance score of 52.71 compared to 17.69, 17.16, and 14.44 for feed flowrate, vacuum pressure intensity, and feed concentration, respectively.
Water constitutes one of the basic necessities of life. Around 71% of the Earth is covered by water, however, not all of it is readily available as fresh water for daily consumption. Fresh water scarcity is a chronic issue which poses a threat to all living things on Earth. Seawater, as a natural resource abundantly available all around the world, is a potential water source to fulfil the increasing water demand. Climate-independent seawater desalination has been touted as a crucial alternative to provide fresh water. While the membrane-based desalination process continues to dominate the global desalination market, the currently employed membrane fabrication materials and processes inevitably bring adverse impacts to the environment. This review aims to elucidate and provide a comprehensive outlook of the recent efforts based on greener approaches used for desalination membrane fabrication, which paves the way towards achieving sustainable and eco-friendly processes. Membrane fabrication using green chemistry effectively minimizes the generation of hazardous compounds during membrane preparation. The future trends and recommendations which could potentially be beneficial for researchers in this field are also highlighted.
Membrane resistance and permselectivity for counter-ions have important roles in determining the performance of cation-exchange membranes (CEMs). In this study, PVA-based polyanions-poly(vinyl alcohol-b-sodium styrene sulfonate)-were synthesized, changing the molar percentages CCEG of the cation-exchange groups with respect to the vinyl alcohol groups. From the block copolymer, poly(vinyl alcohol) (PVA)-based CEMs, hereafter called "B-CEMs", were prepared by crosslinking the PVA chains with glutaraldehyde (GA) solution at various GA concentrations CGA. The ionic transport properties of the B-CEMs were compared with those previously reported for the CEMs prepared using a random copolymer-poly(vinyl alcohol-co-2-acrylamido-2-methylpropane sulfonic acid)-hereafter called "R-CEMs". The B-CEMs had lower water content than the R-CEMs at equal molar percentages of the cation-exchange groups. The charge density of the B-CEMs increased as CCEG increased, and reached a maximum value, which increased with increasing CGA. A maximum charge density of 1.47 mol/dm3 was obtained for a B-CEM with CCEG = 2.9 mol% and CGA = 0.10 vol.%, indicating that the B-CEM had almost two-thirds of the permselectivity of a commercial CEM (CMX: ASTOM Corp. Japan). The dynamic transport number and membrane resistance of a B-CEM with CCEG = 8.3 mol% and CGA = 0.10 vol.% were 0.99 and 1.6 Ωcm2, respectively. The B-CEM showed higher dynamic transport numbers than those of the R-CEMs with similar membrane resistances.
This review discusses the roles of anion exchange membrane (AEM) as a solid-state electrolyte in fuel cell and electrolyzer applications. It highlights the advancement of existing fabrication methods and emphasizes the importance of radiation grafting methods in improving the properties of AEM. The development of AEM has been focused on the improvement of its physicochemical properties, including ionic conductivity, ion exchange capacity, water uptake, swelling ratio, etc., and its thermo-mechano-chemical stability in high-pH and high-temperature conditions. Generally, the AEM radiation grafting processes are considered green synthesis because they are usually performed at room temperature and practically eliminated the use of catalysts and toxic solvents, yet the final products are homogeneous and high quality. The radiation grafting technique is capable of modifying the hydrophilic and hydrophobic domains to control the ionic properties of membrane as well as its water uptake and swelling ratio without scarifying its mechanical properties. Researchers also showed that the chemical stability of AEMs can be improved by grafting spacers onto base polymers. The effects of irradiation dose and dose rate on the performance of AEM were discussed. The long-term stability of membrane in alkaline solutions remains the main challenge to commercial use.
Forward osmosis (FO) has been recognized as the preferred alternative membrane-based separation technology for conventional water treatment technologies due to its high energy efficiency and promising separation performances. FO has been widely explored in the fields of wastewater treatment, desalination, food industry and bio-products, and energy generation. The substrate of the typically used FO thin film composite membranes serves as a support for selective layer formation and can significantly affect the structural and physicochemical properties of the resultant selective layer. This signifies the importance of substrate exploration to fine-tune proper fabrication and modification in obtaining optimized substrate structure with regards to thickness, tortuosity, and porosity on the two sides. The ultimate goal of substrate modification is to obtain a thin and highly selective membrane with enhanced hydrophilicity, antifouling propensity, as well as long duration stability. This review focuses on the various strategies used for FO membrane substrate fabrication and modification. An overview of FO membranes is first presented. The extant strategies applied in FO membrane substrate fabrications and modifications in addition to efforts made to mitigate membrane fouling are extensively reviewed. Lastly, the future perspective regarding the strategies on different FO substrate layers in water treatment are highlighted.
In this study, a magnetic/polyetherimide-acrylonitrile composite nanofiber membrane with effective adsorption of nickel ions in an aqueous solution was created using a simple electrospinning method. Iron oxide nanoparticles (NPs) were stirred and ultrasonically dispersed into a polyetherimide-acrylonitrile solution to create a homogenous NPs suspension, which was placed in an electrospinning machine to produce a uniform and smooth nanofiber composite membrane. Nanoparticle incorporation into this membrane was confirmed using scanning electron microscope, energy dispersive X-ray spectroscopy (EDX), Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and NPs aqueous stability from a leaching test. The high adsorption capability of the membrane on nickel ions was attributed to the combination of magnetic NPs, polyetherimide-acrylonitrile matrix, and the nanostructure of the membrane. A membrane containing magnetic NPs demonstrated the maximum adsorption capabilities (102 mg/g) of nickel ions in an aqueous solution. Various kinetic and isotherm models were applied to understand the adsorption behavior, such as pseudo-second-order kinetic and Langmuir isotherm models. A polyetherimide-acrylonitrile composite nanofiber membrane containing magnetic NPs could be used as an environmentally friendly and nontoxic adsorbent for the removal of nickel ions in an aqueous medium due to its ease of preparation and use and stability in aqueous mediums.
A novel greener MNC/PES membrane was developed through an electrospinning technique for lipase immobilization to catalyze the synthesis of ethyl valerate (EV). In this study, the covalent immobilization of Aspergillus oryzae lipase (AOL) onto an electrospun nanofibrous membrane consisting of magnetic nanocellulose (MNC) and polyethersulfone (PES) to produce EV was statistically optimized. Raman spectroscopy, Fourier-transform infrared spectroscopy: attenuated total reflection, field emission scanning electron microscopy, energy dispersive X-ray spectroscopy, thermal gravimetric analysis (TGA), and differential thermal gravimetric (DTG) of MNC/PES-AOL demonstrated that AOL was successfully immobilized onto the fibers. The Taguchi design-assisted immobilization of AOL onto MNC/PES fibers identified that 1.10 mg/mL protein loading, 4 mL reaction volume, 250 rpm stirring rate, and 50 °C were optimal to yield 72.09% of EV in 24 h. The thermal stability of MNC/PES-AOL was improved by ≈20% over the free AOL, with reusability for up to five consecutive esterification cycles while demonstrating an exceptional half-life of 120 h. Briefly, the electrospun MNC/PES fibers that immobilized AOL showed promising applicability in yielding relatively good EV levels. This study suggests that using MNC as fillers in a PES to improve AOL activity and durability for a longer catalytic process could be a viable option.
Hollow fiber membranes of polyvinylidene fluoride (PVDF) were prepared by incorporating varying concentrations of hydrophilic surface-modifying macromolecules (LSMM) and a constant amount of polyethylene glycol (PEG) additives. The membranes were fabricated by the dry-wet spinning technique. The prepared hollow fiber membranes were dip-coated by hydrophobic surface-modifying macromolecules (BSMM) as the final step fabrication. The additives combination is aimed to produce hollow fiber membranes with high flux permeation and high salt rejection in the matter of seawater desalination application. This study prepares hollow fiber membranes from the formulation of 18 wt. % of PVDF mixed with 5 wt. % of PEG and 3, 4, and 5 wt. % of LSMM. The membranes are then dip-coated with 1 wt. % of BSMM. The effect of LSMM loading on hydrophobicity, morphology, average pore size, surface porosity, and membrane performance is investigated. Coating modification on LSMM membranes showed an increase in contact angle up to 57% of pure, unmodified PVDF/PEG membranes, which made the fabricated membranes at least passable when hydrophobicity was considered as one main characteristic. Furthermore, The PVDF/PEG/4LSMM-BSMM membrane exhibits 161 °C of melting point as characterized by the DSC. This value indicates an improvement of thermal behavior shows so as the fabricated membranes are desirable for membrane distillation operation conditions range. Based on the results, it can be concluded that PVDF/PEG membranes with the use of LSMM and BSMM combination could enhance the permeate flux up to 81.32 kg·m-2·h-1 at the maximum, with stable salt rejection around 99.9%, and these are found to be potential for seawater desalination application.
Electrospun polyacrylonitrile (PAN) nanofiber membrane was functionalized with chitosan and proteins for use in the treatment of dye-containing wastewater. The PAN nanofiber membrane was subjected to alkaline hydrolysis, before being grafted with chitosan and subsequently the proteins from chicken egg white. The resultant nanofiber membrane (P-COOH-CS-CEW) was comprehensively characterized using thermogravimetric analysis, Fourier-transform infrared spectroscopy, and scanning electron microscopy. The efficiency of P-COOH-CS-CEW in removing cationic dye toluidine blue O (TBO) and anionic dye acid orange 7 (AO7) in aqueous solution was evaluated. Based on the performance of model fitting, Langmuir and pseudo-second-order kinetic model could be used to describe the performance of P-COOH-CS-CEW in the removal of TBO (pH 10) and AO7 (pH 2) from the dye solutions. The adsorbed TBO and AO7 dyes can be completely desorbed by an elution solution made of 50% (v/v) ethanol and 1 M sodium chloride. After five consecutive adsorption-desorption cycles, the efficiency of dye removal by P-COOH-CS-CEW was maintained above 97%.
The discharge of massive amounts of oily wastewater has become one of the major concerns among the scientific community. Membrane filtration has been one of the most used methods of treating oily wastewater due to its stability, convenience handling, and durability. However, the continuous occurrence of membrane fouling aggravates the membrane's performance efficiency. Membrane fouling can be defined as the accumulation of various materials in the pores or surface of the membrane that affect the permeate's quantity and quality. Many aspects of fouling have been reviewed, but recent methods for fouling reduction in oily wastewater have not been explored and discussed sufficiently. This review highlights the mitigation strategies to reduce membrane fouling from oily wastewater. We first review the membrane technology principle for oily wastewater treatment, followed by a discussion on different fouling mechanisms of inorganic fouling, organic fouling, biological fouling, and colloidal fouling for better understanding and prevention of membrane fouling. Recent mitigation strategies to reduce fouling caused by oily wastewater treatment are also discussed.