Poly (citric acid)-grafted-MWCNT (PCA-g-MWCNT) was incorporated as nanofiller in polyethersulfone (PES) to produce hemodialysis mixed matrix membrane (MMM). Citric acid monohydrate was polymerized onto the surface of MWCNTs by polycondensation. Neat PES membrane and PES/MWCNTs MMMs were fabricated by dry-wet spinning technique. The membranes were characterized in terms of morphology, pure water flux (PWF) and bovine serum albumin (BSA) protein rejection. The grafting yield of PCA onto MWCNTs was calculated as 149.2%. The decrease of contact angle from 77.56° to 56.06° for PES/PCA-g-MWCNTs membrane indicated the increase in surface hydrophilicity, which rendered positive impacts on the PWF and BSA rejection of the membrane. The PWF increased from 15.8Lm(-2)h(-1) to 95.36Lm(-2)h(-1) upon the incorporation of PCA-g-MWCNTs due to the attachment of abundant hydrophilic groups that present on the MWCNTs, which have improved the affinity of membrane towards the water molecules. For protein rejection, the PES/PCA-g-MWCNTs MMM rejected 95.2% of BSA whereas neat PES membrane demonstrated protein rejection of 90.2%. Compared to commercial PES hemodialysis membrane, the PES/PCA-g-MWCNTs MMMs showed less flux decline behavior and better PWF recovery ratio, suggesting that the membrane antifouling performance was improved. The incorporation of PCA-g-MWCNTs enhanced the separation features and antifouling capabilities of the PES membrane for hemodialysis application.
This work discusses the preparation and characterizations of glass hollow fiber membranes prepared using zeolite-5A as a starting material. Zeolite was formed into a hollow fiber configuration using the phase inversion technique. It was later sintered at high temperatures to burn off organic materials and change the zeolite into glass membrane. A preliminary study, that used thermogravimetric analysis (TGA), X-ray diffraction (XRD), and Fourier transform infrared (FTIR), confirmed that zeolite used in this study changed to glass at temperatures above 1000 °C. The glass hollow fiber membranes prepared using the phase inversion technique has three different microstructures, namely (i) sandwich-like structure that originates from inner layer, (ii) sandwich-like that originates from outer layer, and (iii) symmetric sponge like. These variations were influenced by zeolite weight loading and the flow rate of water used to form the lumen. The separation performances of the glass hollow fiber membrane were studied using the pure water permeability and the rejection test of bovine serum albumin (BSA). The glass hollow fiber membrane prepared from using 48 wt% zeolite loading and bore fluid with 9 mL min(-1) flow rate has the highest BSA rejection of 85% with the water permeability of 0.7 L m(-2) h(-1) bar(-1). The results showed that the separation performance of glass hollow fiber membranes was in the ultrafiltration range, enabled the retention of solutes with molecular sizes larger than 67 kDa such as milk proteins, endotoxin pyrogen, virus, and colloidal silica.
Despite its extraordinary price, ceramic membrane can still be able to surpass polymeric membrane in the applications that require high temperature and pressure conditions, as well as harsh chemical environment. In order to alleviate the high cost of ceramic material that still becomes one of the major factors that contributes to the high production cost of ceramic membrane, various attempts have been made to use low cost ceramic materials as alternatives to well-known expensive ceramic materials such as alumina, silica, and zirconia in the fabrication of ceramic membrane. Thus, local Malaysian kaolin has been chosen as the ceramic material in this study for the preparation of kaolin hollow fibre membrane since it is inexpensive and naturally abundant in Malaysia. Due to the fact that the sintering process plays a prominent role in obtaining the desired morphology, properties, and performances of prepared ceramic membrane, the aim of this work was to study the effect of different sintering temperatures applied (ranging from 1200 to 1500 °C) in the preparation of kaolin hollow fibre membrane via dry/wet phase inversion-based spinning technique and sintering process. The morphology and properties of membrane were then characterised by SEM, AFM, FTIR, XRD, and three-point bending test, while the performances of membrane were investigated by conducting water permeation and Reactive Black 5 (RB5) dye rejection tests. From the experimental results obtained, the sintering temperature of 1400 °C could be selected as the optimum sintering temperature in preparing the kaolin hollow fibre membrane with the dense sponge-like structure of separation layer that resulted in the good mechanical strength of 70 MPa with the appreciable water permeation of 75 L/h m(2) bar and RB5 rejection of 68%.
A novel approach in the design of a safe, high performance hemodialysis membrane is of great demand. Despite many advantages, the employment of prodigious nanomaterials in hemodialysis membrane is often restricted by their potential threat to health. Hence, this work focusses on designing a biocompatible polyethersulfone (PES) hemodialysis membrane embedded with poly (citric acid)-grafted-multi walled carbon nanotubes (PCA-g-MWCNTs). Two important elements which could assure the safety of the nanocomposite membrane, i.e. (i) dispersion stability and (ii) leaching of MWCNTs were observed. The results showed the improved dispersion stability of MWCNTs in water and organic solvent due to the enriched ratio of oxygen-rich groups which subsequently enhanced membrane separation features. It was revealed that only 0.17% of MWCNTs was leached out during the membrane fabrication process (phase inversion) while no leaching was detected during permeation. In terms of biocompatibility, PES/PCA-g-MWCNT nanocomposite membrane exhibited lesser C3 and C5 activation (189.13 and 5.29ng/mL) and proteins adsorption (bovine serum albumin=4.5μg/cm2, fibrinogen=15.95μg/cm2) as compared to the neat PES membrane, while keeping a normal blood coagulation time. Hence, the PES/PCA-g-MWCNT nanocomposite membrane is proven to have the prospect of becoming a safe and high performance hemodialysis membrane.
This work describes the development of supported zeolite-Y membranes, prepared using the hydrothermal method, for the removal of nickel from an aqueous solution. Alumina hollow fibers prepared using the phase inversion and sintering technique were used as an inert support. The supported zeolite-Y membranes were characterized using the field emission scanning electron microscope (FESEM), X-ray diffraction (XRD), and the water permeation and rejection test. The performance of the supported zeolite-Y membranes for heavy metal removal using batch adsorption and filtration test was studied using the atomic absorption spectroscopy (AAS). The adsorption study shows that the removal of nickel was pH-dependent but affected by the presence of α-alumina. The seeded zeolite-Y membrane gave the highest adsorption capacity which was 126.2 mg g-1. This enabled the membrane to remove 63% of nickel ions from the aqueous solution within 180 min of contact time. The adsorption mechanism of nickel onto the zeolite-Y membrane was best fitted to the Freundlich isotherm. The kinetic study concluded that the adsorption was best fitted to pseudo-second-order model with higher correlation coefficient (R2 = 0.9996). The filtration study proved that the zeolite-Y membrane enabled to reduce the concentration of heavy metal at parts per billion level.
Separation and purification of oilfield produced water (OPW) is a major environmental challenge due to the co-production of the OPW during petroleum exploration and production operations. Effective capture of oil contaminant and its in-situ photodegradation is one of the promising methods to purify the OPW. Based on the photocatalytic capability of graphitic carbon nitride (GCN) which was recently rediscovered, photodegradation capability of GCN for OPW was investigated in this study. GCN was synthesized by calcination of urea and further exfoliated into nanosheets. The GCNs were incorporated into polyacrylonitrile nanofibers using electrospinning, which gave a liquid-permeable self-supporting photocatalytic nanofiber mat that can be handled by hand. The photocatalytic nanofiber demonstrated 85.4% degradation of OPW under visible light irradiation, and improved the degradation to 96.6% under UV light. Effective photodegradation of the photocatalytic nanofiber for OPW originates from synergetic effects of oil adsorption by PAN nanofibers and oil photodegradation by GCNs. This study provides an insight for industrial application on purification of OPW through photocatalytic degradation under solar irradiation.
Palm oil fuel ash (POFA) is an agricultural waste which was employed in this study to produce novel adsorptive ceramic hollow fibre membranes. The membranes were fabricated using phase inversion-based extrusion technique and sintered at 1150 °C. The membranes were then evaluated on their ability to adsorb cadmium (Cd(II)). These membranes were characterised using (nitrogen) N2 adsorption-desorption analysis, field emission scanning electron microscopy-energy-dispersive X-ray spectroscopy (FESEM-EDX) mapping, X-ray fluorescence (XRF), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR) analyses while adsorptivity activity was examined by batch adsorption studies. The adsorption test results show that the quantity of hollow fibre used and water pH level significantly affected the adsorption performance with the 3-fibre membrane yielding 96.4% Cd(II) removal in 30 min equilibrium time at pH 7. These results are comparable to those reported by other studies, and hence demonstrate a promising alternative of low-cost hollow fibre adsorbent membrane. Graphical abstract Figure of FESEM image of the hollow fibre, proposed mechanism and the graph of percentage removal of Cd(II) using POFA.
Hydrothermal method has been proven to be an effective method to synthesise the nanostructured titanium dioxide (TiO2) with good morphology and uniform distribution at low temperature. Despite of employing a well-known and commonly used glass substrate as the support to hydrothermally synthesise the nanostructured TiO2, this study emphasised on the application of kaolin hollow fibre membrane as the support for the fabrication of kaolin/TiO2 nanorods (TNR) membrane. By varying the hydrothermal reaction times (2 h, 6 h, and 10 h), the different morphology, distribution, and properties of TiO2 nanorods on kaolin support were observed by field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDX), atomic force microscope (AFM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). It was found that the well-dispersed of TiO2 nanorods have improved the surface affinity of kaolin/TNR membrane towards water, allowing kaolin/TNR membrane prepared from 10 h of hydrothermal reaction to exhibit the highest water permeation of 165 L/h.m2.bar. In addition, this prepared membrane also showed the highest photocatalytic activity of 80.3% in the decolourisation of reactive black 5 (RB5) under UV irradiation. On top of that, the kaolin/TNR membrane prepared from 10 h of hydrothermal reaction also exhibited a good resistance towards photocorrosion, enabling the reuse of this membrane for three consecutive cycles of photocatalytic degradation of RB5 without showing significant reduction in photocatalytic efficiency towards the decolourisation of RB5.
Adsorption is one of the most efficient ways to remove heavy metal from wastewater. In this study, the adsorptive removal of hexavalent chromium, Cr (VI) from aqueous solution was investigated using natural zeolite, clinoptilolite, in the form of hollow fibre ceramic membrane (HFCM). The HFCM sample was prepared using phase inversion-based extrusion technique and followed by sintering process at different sintering temperatures in the range of 900-1050 °C. The fabricated HFCM was characterised using scanning electron microscopy (SEM), contact angle, water permeability, and mechanical strength for all HFCMs sintered at different temperatures. The adsorption and filtration test of Cr (VI) were performed using an in-house water permeation set up with a dead-end cross-flow permeation test. An asymmetric structure with sponge- and finger-like structures across the cross-section of HFCM was observed using SEM. Based on the characterisation data, 1050 °C was chosen to be the best sintering temperature as the water permeability and mechanical strength of this HFCM were 29.14 L/m2∙h and 50.92 MPa, respectively. The performance of the HFCM in adsorption/filtration was 44% of Cr (VI) removal at the Cr (VI) concentration of 40 mg/L and pH 4. In addition, the mathematical model was also performed in simulating the experimental data obtained from this study. All in all, the natural zeolite-based HFCM has a potential as a single-step Cr (VI) removal by membrane adsorption for the wastewater treatment.
Portable dialysis is a need to implement daily and nocturnal hemodialysis. To realize portable dialysis, a dialysate regeneration system comprising superior adsorbents is required to regenerate the used dialysate. This study aims to develop a nano-adsorbent, derived from corn starch for urea removal. Oxidized starch nanoparticles (oxy-SNPs) were prepared via liquid phase oxidation, followed by chemical dissolution and non-solvent precipitation. The oxy-SNPs possessed Z-average size of 177.7 nm with carbonyl and carboxyl contents of 0.068 and 0.048 per 100 glucose units, respectively. The urea adsorption achieved the equilibrium after 4 h with 95% removal. The adsorption mechanism fitted Langmuir isotherm while the adsorption kinetics obeyed pseudo-second-order model. This new material has a maximum adsorption capacity of 185.2 mg/g with a rate constant of 0.04 g/mg.h. Moreover, the oxy-SNPs exhibited the urea uptake recovery of 91.6%. Oxy-SNPs can become a promising adsorbent for dialysate regeneration system to remove urea.
Polyurethane (PU) with three different functional groups: carboxyl, hydroxyl and sulphonyl group on its molecular structure were synthesised in this work. The synthesised material suppresses blood clotting and exhibits anticoagulant characteristics due to the presence of the important anionic groups. The synthesised PU was blended with polyethersulphone (PES) and fabricated into flat-sheet membrane to study the physico-chemical and biocompatibility properties of the PES membrane for blood purification application. PES-PU flat-sheet membranes were fabricated via the dry-wet phase separation technique. Different loading of PU (0, 1, 2, 3, 4, and 5%) blended with PES was studied and compared. Based on the in-vitro biocompatibility analysis of the membrane, it can be suggested that the membrane incorporated with PU has better anticoagulant properties compared to the pristine PES membrane. PU incorporation prolonged the clotting time, decreased the formation of thrombin, decreased soluble complement component 3a (C3a) generation and suppressed platelet adhesion and aggregation. The anionic groups on the membrane surface might bind to coagulation factors (antithrombin) and the calcium ions, Ca2+ and thus improve anticoagulant ability. Based on both physico-chemical and in-vitro studied, 4% loading of PU is the optimum loading for incorporation with PES membrane. These results suggested that the blended PES-PU membranes with good haemocompatibility allowed practical application in the field of blood purification.
Comparison studies in suspension and hybrid photocatalytic membrane reactor (HPMR) system was investigated by using Reactive Black 5 (RB5) as target pollutant under UVA light irradiation. To achieve this aim, hybrid TiO2/clinoptilolite (TCP) photocatalyst powder was prepared by solid-state dispersion (SSD) methods and embedded at the outer layer of dual layer hollow fiber (DLHF) membranes fabricated via single step co-spinning process. TiO2 and CP photocatalyst were also used as control samples. The samples were characterized by Scanning Electron Microscopy (SEM), Energy Dispersion of X-ray (EDX), X-ray diffraction (XRD) and Brunauer-Emmett-Teller (BET) analyses. The result shows that TCP was actively functioned as photocatalyst in suspension system and 86% of RB5 photocatalytic degradation achieved within 60 min; however the additional step is required to separate the catalyst with treated water. In the HPMR system, even though the RB5 photocatalytic degradation exhibits lower efficiency however the rejection of RB5 was achieved up to 95% under UV irradiation due to the properties of photocatalytic membranes. The well dispersed of TCP at the outer layer of DLHF membrane have improved the surface affinity of DL-TCP membrane towards water, exhibit the highest pure water flux of 41.72 L/m2.h compared to DL-TiO2 membrane. In general, CP can help on improving photocatalytic activity of TiO2 in suspension, increased the RB5 removal and the permeability of DLHF membrane in HPMR system as well.
In this work, the novel imprinted zeolite (IZ) was synthesized, and its properties and performance in terms of adsorption of p-Cresol, which represent the protein-bounded uremic toxins in aqueous phase under phosphate buffer saline, were studied and compared with the synthesized zeolite-Y (ZeoY-S) and commercial CBV 100 zeolite-Y (ZeoY-C). The ZeoY-S was synthesized from sodium aluminate, NaOH, H2O and SiO2 under aging for 24 h at room temperature and hydrothermal condition for 24 h at 100 °C, with an initial composition of 10SiO2:Al2O3:4Na2O:180H2O. The ZeoY-S has been modified by using the imprinting technology to produce the IZ via the use of p-Cresol as a template. The p-Cresol successfully imprinted on the zeolite-Y was proved through the multipoint Brunauer-Emmett-Teller (BET) and the performance of IZ that was compared to ZeoY-S and ZeoY-C. Based on the BET results, it proves that the pore size of IZ is in accordance with the target compound, which is p-Cresol at 0.79 nm. This modification was able to adsorb p-Cresol 2.5 and 3.5 times higher than ZeoY-S and ZeoY-C can, respectively. Langmuir and Freundlich adsorption isotherm models, together with the pseudo-first and -second order and intra-particle diffusion kinetics models, were used to investigate the adsorption behavior of p-Cresol on the zeolites. The IZ has 4.30 times greater competitive molecules than ZeoY-S and the properties of IZ were not influenced by the content of other phenolic group uremic toxins as competitive molecules. It can be concluded that the micropores of zeolite as adsorbent can be modified using the imprinting technology in order to increase its sensitivity and selectivity towards p-Cresol.
Methylene blue (MB) is a dye pollutant commonly present in textile wastewater. We investigate and critically evaluate the applicability of BaTiO3/GO composite for photodegradation of MB in synthetic wastewater under UV-vis irradiation. To enhance its performance, the BaTiO3/GO composite is varied based on the BaTiO3 weight. To compare and evaluate any changes in their morphologies and crystalline structures before and after treatment, BET (Brunauer-Emmett-Teller), XRD (X-ray diffraction), FTIR (Fourier transform infrared spectroscopy), SEM (scanning electron microscopy) and TEM (transmission electron microscopy) tests are conducted, while the effects of reaction time, pH, dose of photocatalyst and initial MB concentration on its photodegradation by the composite are also investigated under identical conditions. The degradation pathways and removal mechanisms of MB by the BaTiO3/GO are elaborated. It is evident from this study that the BaTiO3/GO composite is promising for MB photodegradation through ·OH. Under optimized conditions (0.5 g/L of dose, pH 9.0, and 5 mg/L of MB concentration), the composite with 1:2 dose ratio of BaTiO3/GO has the highest MB degradation rate (95%) after 3 h of UV vis irradiation. However, its treated effluents still could not comply with the discharge standard limit of less than 0.2 mg/L imposed by national environmental legislation. This suggests that additional biological treatments are still required to deal with the remaining oxidation by-products of MB, still present in the wastewater samples such as 3,7-bis (dimethyl-amino)-10H-phenothiazine 5-oxide.
The contribution of palm oil fuel ash (POFA), an agricultural waste as a low cost adsorbent for the removal of arsenite (As(III)) and arsenate (As(V)) was explored. Investigation on the adsorbency characteristics of POFA suspension revealed that the surface area, particle size, composition, and crystallinity of the SiO2 rich mullite structure were the crucial factors in ensuring a high adsorption capacity of the ions. Maximum adsorption capacities of As(III) and As(V) at 91.2 and 99.4 mg g-1, respectively, were obtained when POFA of 30 μm particle size was employed at pH 3 with the highest calcination temperature at 1150 °C. An optimum dosage of 1.0 g of dried POFA powder successfully removed 48.7% and 50.2% of As(III) and As(V), respectively. Molecular modeling using the density functional theory consequently identified the energy for the proposed reaction routes between the SiO- and As+ species. The high stability of the POFA suspension in water in conjunction with good adsorption capacity of As(III) and As(V) seen in this study, thus envisages its feasibility as a potential alternative absorbent for the remediation of water polluted with heavy metals.
Bisphenol A (BPA) is a refractory pollutant presents in water body that possesses serious threats to living organisms. To deal with it, we investigate and evaluate the effectiveness of GO@BiOI/Bi2WO6 composite as a novel photocatalyst for BPA removal from aqueous solutions under UV-vis irradiation. To enhance its removal for BPA, the surface of BiOI/Bi2WO6 is modified with graphene oxide (GO). This composite is named as 'GO@BiOI/Bi2WO6'. Changes in its physico-chemical properties after surface modification with GO are characterized by XRD, FTIR, FESEM-EDS, XPS, PL, and BET methods. Optimized conditions of BPA degradation by the composite are determined under identical conditions. Photodegradation pathways of BPA and its removal mechanisms by the same composite are presented. It is obvious that the GO@BiOI/Bi2WO6 has demonstrated its potential as a promising photocatalyst for BPA removal under UV-vis irradiation. About 81% of BPA removal is attained by the GO@BiOI/Bi2WO6 under optimized conditions (10 mg/L of BPA, 0.5 g/L of dose, pH 7 and 5 h of reaction time). The oxidation by-products of BPA degradation include p-hydroquinone or 4-(1-hydroxy-1-methyl-ethyl)-phenol. In spite of its performance, the treated effluents are still unable to meet the maximum discharge limit of <1 mg/L set by national legislation. Therefore, subsequent biological processes are essential to maximize its biodegradation in the wastewater samples before their discharge into waterbody.
This study aimed to examine the impact of BPA exposure on pregnancy and foetuses on cardiac tissues and the expression of cardiac microRNAs (miRNAs) related to heart development and diseases. Pregnancy is known to be the "critical windows" in determining the offspring physical and cells development in their life after birth. The increment of the risk of cardiovascular disease (CVD) in a later stage of life has been reported by few studies demonstrated from prenatal exposure of BPA. BPA has been shown to alter miRNAs expression profiles for organ development, regeneration and metabolic functions. These alterations have been associated with the risk of CVDs. However, the associations between pregnancy outcomes and miRNAs expression in cardiac of mother- and foetuses-exposed to BPA are still not entirely explored. In BPA-exposed pregnant rat groups, a significant weight gained was observed in comparison to control (p
Natural zeolite is widely used in removing ammonia via adsorption process because of its superior ion-exchange properties. Ceramic particle size affects the adsorptivity of particles toward ammonia. In this study, hollow fiber ceramic membrane (HFCM) was fabricated from natural zeolite via phase inversion. The effect of natural zeolite particle size toward the properties and performance of HFCM was evaluated. The results show that the HFCM with smaller particle sizes exhibited a more compact morphological structure with better mechanical strength. The adsorption performance of HFCM was significantly improved with smaller particle sizes because of longer residence time, as proven by the lower water permeability. A high adsorption performance of 96.67% was achieved for HFCM with the smallest particle size (36 μm). These findings provide a new perspective on the promising properties of the natural zeolite-derived HFCM for ammonia removal.
In this study, improvement of urea and creatinine permeability of polyethersulfone (PES) membrane by coating with synthesized tripolyphosphate-crosslinked chitosan (TPP-CS) has been conducted. Original and modified membranes, e.g. pristine PES, polyethersulfone-polyethylene glycol (PES-PEG) and PES-PEG/TPP-CS membranes were characterized using FTIR, DTG, SEM, AFM, water uptake, contact angles, porosity measurement, tensile strength test and permeation tests against urea and creatinine. The results show that the PES modification by TPP-CS coating has been successfully carried out. The water uptake ability, hydrophilicity and porosity of the modified membranes increase significantly to a greater degree. All modified membranes have good thermal stability and tensile strength and their permeation ability towards urea and creatinine increase with the increasing concentration of TPP-CS. PES membrane has urea clearance ability of 7.36 mg/dL and creatinine of 0.014 mg/dL; membrane PES-PEG shows urea clearance of 11.87 mg/dL and creatinine of 0.32 mg/dL; while PES-PEG/TPP-CS membrane gives urea clearance of 20.87-36.40 mg/dL and creatinine in the range of 0.52-0.78 mg/dL. These results suggest that the PES-PEG membrane coated with TPP-CS is superior and can be used as potential material for hemodialysis membrane.
The development of wearable artificial kidney demands an efficient dialysate recovery, which relies upon the adsorption process. This study proposes a solution to solve the problem of competitive adsorption between the uremic toxins by employing two adsorptive components in a membrane separation process. Dual-layer hollow fiber (DLHF) membranes, which are composed of a polysulfone (PSf)/activated carbon (AC) inner layer and a PSf/poly(methyl methacrylate) (PMMA) outer layer, were prepared for co-adsorptive removal of creatinine and urea from aqueous solution. The DLHF membranes were characterized in terms of morphological, physicochemical, water transport, and creatinine adsorption properties. The membrane was then subjected to an ultrafiltration adsorption study for performance evaluation. The incorporation of AC in membrane, as confirmed by microscopic and surface analyses, has improved the pure water flux up to 25.2 L/(m2 h). A membrane with optimum AC loading (9 wt %) demonstrated the highest maximum creatinine adsorption capacity (86.2 mg/g) based on the Langmuir adsorption isotherm model. In the ultrafiltration adsorption experiment, the membrane removed creatinine and urea with a combined average percent removal of 29.3%. Moreover, the membrane exhibited creatinine and urea uptake recoveries of 98.8 and 81.2%, respectively. The combined action of PMMA and AC in the PSf DLHF membrane has made the adsorption of multiple uremic toxins possible during dialysate recovery.